Monomers and composition which can be crosslinked and crosslinked polymers

ABSTRACT

PCT No. PCT/EP95/04359 Sec. 371 Date May 14, 1997 Sec. 102(e) Date May 14, 1997 PCT Filed Nov. 6, 1995 PCT Pub. No. WO96/16008 PCT Pub. Date May 30, 1996Compounds of the formula I(A)n-B(I)in which A is the radical of a strained cycloolefin, B is a direct bond or an n-valent bridging group and n is an integer from 2 to 8, with the exception of 1,2-bisnorbornenyl-ethane and norbornenecarboxylic acid norbornenemethyl ester. The compounds of the formula I can be polymerized with one-component catalysts (ring-opening metathesis polymerization).

The present invention relates to compounds having at least two strainedcycloolefins bonded directly or via a bridging group; compositionscomprising these compounds and a one-component catalyst for thermallyinduced and/or radiation-induced metathesis polymerization; apolymerization process, crosslinked polymers from the compoundsmentioned and, if appropriate, other olefins and/or cycloolefinssuitable for metathesis polymerization; carrier materials coated withthese crosslinked polymers; and a polymerization process.

WO 93/13171 describes air- and water-stable one-component andtwo-component catalysts based on molybdenum compounds and tungstencompounds containing carbonyl groups and ruthenium compounds and osmiumcompounds with at least one polyene ligand for the thermal metathesispolymerization and a photoactivated metathesis polymerization ofstrained cycloolefins, in particular norbornene and norbornenederivatives. No other polycyclic--above all non-fused polycycliccycloolefins are mentioned. The one-component catalysts of the rutheniumcompounds used, that is to say [(C₆ H₆) Ru(CH₃ CN)₂ Cl]⁺ PF₆ ⁻ and[Ru(cumene)Cl₂ ]₂, can indeed be activated by UV irradiation; however,the storage stability of the compositions with norbornene are [sic]completely inadequate. These catalysts are capable of replacing theknown two-component catalysts only inadequately.

Demonceau et al. [Demonceau, A., Noels A. F., Saive, E., Hubert, A. J.,J. Mol. Catal. 76:123-132(1992)] describe (C₆ H₅)₃ ]₃ PRuCl₂ [sic],(p-cumene)RuCl₂ P(C₆ H₁₁)₃ and (C₆ H₅)₃ ]₃ PRuHCl [sic] as thermalcatalysts for ring-opening metathesis polymerization of norbornene, afused polycycloolefin. These catalysts have not found acceptance inindustrial preparation because their activity is too low. It istherefore proposed to increase the activity by the addition of diazoesters. It is also mentioned that only (p-cumene)RuCl₂ P(C₆ H₁₁)₃ iscapable of polymerizing norbornene in a relatively short time at 60° C.Cyclooctene is also mentioned as a further monomer. No othercycloolefins for methatesis [sic] polymerization are mentioned.

Petasis and Fu [Petasis, N. A., Fu, D., J. Am. Chem. Soc. 115:7208-7214(1993)] describe thermal ring-opening metathesis polymerization ofnorbornene usingbiscyclopentadienyl-bis(trimethylsilyl)methyl-titanium(IV) as athermally active catalyst. No other cycloolefins for metathesispolymerization are mentioned. EP 287,762 describes crosslinkedcopolymers of a mixture of 1,2-bisnorbornenyl-ethane of the formula##STR1## and a compound of the fromula [sic] ##STR2## which are preparedusing catalyst systems for thermal metathesis polymerization comprisinga catalyst and an activator. A disadvantage of these systems is the needto separate the catalyst and activator, so that no storage-stablepolymerizable compositions can be provided. The catalyst and activatorcan be combined only directly before the polymerization, highly reactivecompositions which rapidly gel with evolution of heat being formed. Theproduction of shaped articles is therefore limited to certain processes,such as, for example, the RIM process. The resulting crosslinkedpolymers have high softening temperatures. No coated materials arementioned.

It has now been found that compositions of compounds comprising at leasttwo strained cycloolefins bonded directly or via a bridge group and aone-component catalyst are storage-stable and have an outstandingprocessability, even in the presence of oxygen and moisture, dependingon the choice of catalyst. These compositions can be processed by meansof the most diverse shaping processes to give crosslinked metathesispolymers without special safety precautions. The polymers have highcrosslinking densities and outstanding mechanical and electricalproperties as well as surface properties, for example low ε values andtan δ values, and a very low absorption of water. The monomers used areoutstanding film-forming agents and the polymer films have outstandingproperties. It has furthermore been found that coatings in the form ofcrosslinked polymers which have exceptionally high adhesive strengthseven on smooth metal surfaces are obtained with the compositions. Thestorage stability enables the use as coatings, paints, photoresists andadhesives and the production of all types of shaped articles. Thepreparation of rubber-like or thermoplastic polymers which can becrosslinked further is also possible.

The invention relates to compounds of the formula I

    (A).sub.n --B                                              (I),

in which A is the radical of a strained cycloolefin, B is a direct bondor an n-valent bridging group and n is an integer from 2 to 8, with theexception of 1,2-bisnorbornenyl-ethane and norbornenecarboxylic acidnorbornenemethyl ester.

The cyclic olefins can be monocyclic or polycyclic fused and/or bridgedring systems, for example with two to four rings, which areunsubstituted or substituted and can contain heteroatoms, such as, forexample, O, S, N or Si, in one or more rings and/or fused alicyclic,aromatic or heteroaromatic rings, such as, for example,o-cyclopentylene, o-phenylene, o-naphthylene, o-pyridinylene oro-pyrimidinylene. The individual cyclic rings can contain 3 to 16,preferably 3 to 12, and particularly preferably 3 to 8 ring members. Thecyclic olefins can contain other non-aromatic double bonds, preferably 2to 4 such additional double bonds, depending on the ring size. The ringsubstituents are those which are inert, i.e. which do not impair thechemical stability of the one-component catalysts.

Fused-on alicyclic rings preferably contain 3 to 8, particularlypreferably 4 to 7, and especially preferably 5 or 6 ring C atoms.

In a preferred embodiment, the radicals a in formula I correspond tocycloolefin radicals of the formula II ##STR3## in which Q₁ is a radicalhaving at least one carbon atom which, together with the --CH═CQ₂ group,forms an at least 3-membered alicyclic ring which optionally containsone or more heteroatoms chosen from the group consisting of silicon,phosphorus, oxygen, nitrogen and sulfur; and which is unsubstituted orsubstituted by halogen, ═O, --CN, --NO₂, R₁ R₂ R₃ Si--(O)_(u) --,--COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₂₀ alkyl, C₁ -C₂₀ hydroxyalkyl, C₁ -C₂₀ haloalkyl, C₁-C₆ cyanoalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁ -₁₆ aryl, C₇ -C₁₆ aralkyl, C₃-C₆ heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆ heteroaralkyl or R₄-X-; or in which two adjacent C atoms are substituted by --CO--O--CO--or --CO--NR₅ --CO--; or in which an aromatic or heteroaromatic ringand/or further alicyclic rings which is [sic] unsubstituted orsubstituted by halogen, --CN, --NO₂, R₆ R₇ R₈ Si--(O)_(u) --, --COOM,--SO₃ M,--PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁-C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₁ -C₆ cyanoalkyl,C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇ -C₁₆ aralkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆ heteroaralkyl or R₁₃ -X₁ -are optionally fused onto adjacent carbon atoms of the alicyclic ring;

X and X₁ independently of one another are --O--,--S--, --CO--, --SO--,-SO₂ --, --O--C(O)--, --C(O)--O--, --C(O)--NR₅ --, --NR₁₀ --C(O)--,--SO₂ --O-- or --O--SO₂ --;

R₁, R₂ and R₃ independently of one another are C₁ -C₁₂ alkyl,C₁ -C₁₂perfluoroalkyl, phenyl or benzyl;

R₄ and R₁₃ independently are C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl or C₇ -C₁₆ aralkyl;

R₅ and R₁₀ independently of one another are hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl, where the alkyl groups in turn are unsubstituted orsubstituted by C₁ -C₁₂ alkoxy or C₃ -C₈ cycloalkyl;

R₆, R₇ and R₈ independently of one another are C₁ -C₁₂ alkyl, C₁ -C₁₂perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal; and

u is 0 or 1;

where the alicyclic ring formed with Q₁ optionally contains furthernon-aromatic double bonds;

Q₂ is hydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₁₂ alkoxy,halogen, --CN or R₁₁ -X₂ ;

R₁₁ is C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈cycloalkyl, C₆ -C₁₆ aryl or C₇ -C₁₆ aralkyl;

X₂ is --C(O)--O-- or --C(O)--NR₁₂ --;

R₁₂ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

where the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl,aralkyl and heteroaralkyl groups are unsubstituted or substituted by C₁-C₁₂ alkyl, C₁ -C₁₂ alkoxy, --NO₂, --CN or halogen, and where theheteroatoms of the abovementioned heterocycloalkyl, heteroaryl andheteroaralkyl groups are chosen from the group consisting of --O--,--S--, --NR₉ -- and --N═; and

R₉ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl.

The position of the double bond in the ring of the formula II inrelation to the free bond essentially depends on the ring size and thepreparation method for the compounds of the formula I.

If an asymmetric centre is present in the compounds of the formula II,the compounds can occur in optically isomeric forms as a result. Somecompounds of the formula II can occur in tautomeric forms (for exampleketo-enol tautomerism). If an aliphatic C═C double bond is present,geometric isomerism (E form or Z form) can also occur. Exo-endoconfigurations are furthermore also possible. Formula II thus includesall the possible stereoisomers which are present in the form ofenantiomers, tautomers, diastereomers, E/Z isomers or mixtures thereof.

In the definitions of the substituents, the alkyl, alkenyl and alkynylgroups can be straight-chain or branched. The same also applies to thealkyl moiety or each alkyl moiety of alkoxy, alkylthio, alkoxycarbonyland further alkyl-containing groups. These alkyl groups preferablycontain 1 to 12, more preferably 1 to 8, and particularly preferably 1to 4 C atoms. These alkenyl and alkynyl groups preferably contain 2 to12, more preferably 2 to 8, and particularly preferably 2 to 4 C atoms.

Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl and the various isomericpentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl andeicosyl radicals.

Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl,1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl,1-hydroxy-iso-butyl, 1-hydroxy-sec-butyl, 1-hydroxy-tert-butyl and thevarious isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl and eicosyl radicals.

Haloalkyl includes, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyland halogenated, in particular fluorinated or chlorinated, alkanes, suchas, for example, the isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyland tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl,3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl,n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl andn-octadec-4-enyl.

Cycloalkyl is preferably C₅ -C₈ cycloalkyl, in particular C₅ - or C₆cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropyl,cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl andcyclooctyl.

Cyanoalkyl includes, for example, cyanomethyl (methylnitrile),cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl,2-cyano-n-butyl, 1-cyano-iso-butyl, 1-cyano-sec-butyl,1-cyano-tert-butyl and the various isomeric cyanopentyl and -hexylradicals.

Aralkyl preferably contains 7 to 12 C atoms, and particularly preferably7 to 10 C atoms. It can be, for example, benzyl, phenethyl,3-phenylpropyl, α-methylbenzyl, phenbutyl or α,α-dimethylbenzyl.

Aryl preferably contains 6 to 10 C atoms. It can be, for example,phenyl, pentalin, indene, naphthalene, azulene or anthracene.

Heteroaryl preferably contains 4 or 5 C atoms and one or two heteroatomsfrom the group consisting of O, S and N. It can be, for example,pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine,pyrimidine, pyridazine, indole, purine or quinoline.

Heterocycloalkyl preferably contains 4 or 5 C atoms and one or twoheteroatoms from the group consisting of O, S and N. It can be, forexample, oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine,piperidine, piperazine, morpholine, tetrahydrofuran ortetrahydrothiophene.

Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy,n-butyloxy, i-butyloxy, sec-butyloxy or t-butyloxy.

Alkali metal in the context of the present invention is to be understoodas meaning lithium, sodium, potassium, rubidium and caesium, inparticular lithium, sodium and potassium.

Alkaline earth metal in the context of the present invention is to beunderstood as meaning beryllium, magnesium, calcium, strontium andbarium, in particular magnesium and calcium.

In the above definition, halogen is to be understood as meaningfluorine, chlorine, bromine and iodine, preferably fluorine, chlorineand bromine.

In the radicals of the formula II, Q₂ is preferably hydrogen.

Compounds with radicals of the formula II which are furthermorepreferred are those in which the alicyclic ring which Q₁ forms togetherwith the --CH═CQ₂ -- group has 3 to 16, more preferably 3 to 12, andparticularly preferably 3 to 8 ring atoms, where the fused ring systemcan be monocyclic, bicyclic, tricyclic or tetracyclic.

The process according to the invention can be carried out particularlyadvantageously with those compounds with radicals of the formula II inwhich

Q₁ is a radical with at least one carbon atom which, together with the--CH═CQ₂ -- group, forms a 3- to 20-membered alicyclic ring whichoptionally contains one or more heteroatoms chosen from the groupconsisting of silicon, oxygen, nitrogen and sulfur; and which isunsubstituted or substituted by halogen, ═O, --CN, --NO₂, R₁ R₂ R₃Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁).sub._(1/2), --SO₃(M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂hydroxyalkyl, C₁ -C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇-C₁₂ aralkyl, C₃ -C₆ heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₁₂heteroaralkyl or R₄ -X-; or in which two adjacent C atoms in thisradical Q₁ are substituted by --CO--O--CO-- or --CO--NR₅ --CO--; or inwhich an aromatic or heteroaromatic ring and/or further alicyclic ringswhich are unsubstituted or substituted by halogen, --CN, --NO₂, R₆ R₇ R₈Si--, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₁₂ alkyl, C₁ -C₁₂ -haloalkyl C₁ -C₄ cyanoalkyl, C₃ -C₆cycloalkyl, C₆ -C₁₂ aryl, C₇ -C₁₂ aralkyl, C₃ -C₆ heterocycloalkyl, C₃-C₁₂ heteroaryl, C₄ -C₁₂ heteroaralkyl or R₁₃ -X₁ - are optionally fusedonto adjacent carbon atoms;

X and X₁ independently of one another are --O--, --S--, --CO--, --SO--,--SO₂ --, --O--C(O)--, --C(O)--O--, --C(O)--NR₅ --, --NR₁₀ --C(O)--,--SO₂ --O-- or --O--SO₂ --; and

R₁, R₂ and R₃ independently of one another are C₁ -C₆ alkyl, C₁ -C₆perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal;

R₄ and R₁₃ independently of one another are C₁ -C₁₂ alkyl, C₁ -C₁₂haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₂ aryl or C₇-C₁₂ aralkyl;

R₅ and R₁₀ independently of one another are hydrogen, C₁ -C₆ alkyl,phenyl or benzyl, where the alkyl groups in turn are unsubstituted orsubstituted by C₁ -C₆ alkoxy or C₃ -C₆ cycloalkyl;

R₆, R₇ and R₈ independently of one another are C₁ -C₆ alkyl, C₁ -C₆perfluoroalkyl, phenyl or benzyl;

u is 0 or 1;

where the alicyclic ring formed with Q₁ optionally contains furthernon-aromatic double bonds;

Q₂ is hydrogen, C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₆ alkoxy,halogen, --CN or R₁₁ -X₂ -;

R₁₁ is C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₆cycloalkyl, C₆ -C₁₂ aryl or C₇ -C₁₂ aralkyl;

X₂ is --C(O)--O-- or --C(O)--NR₁₂ ; and

R₁₂ is hydrogen, C₁ -C₆ alkyl, phenyl or benzyl;

and where the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyland heteroaralkyl groups are unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ alkoxy, --NO₂, --CN or halogen, and where the heteroatomsof the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosenfrom the group consisting of --O--, --S--, --NR₉ - and --N═; and R₉ ishydrogen, C₁ -C₆ alkyl, phenyl or benzyl.

Preferred compounds with a radical of the formula II from this group arethose in which

Q₁ is a radical with at least one carbon atom which, together with the--CH═CQ₂ - group, forms a 3- to 10-membered alicyclic ring whichoptionally contains a heteroatom chosen from the group consisting ofsilicon, oxygen, nitrogen and sulfur and is unsubstituted or substitutedby halogen, --CN, --NO₂, R₁ R₂ R₃ Si--, --COOM, --SO₃ M, --PO₃ M,--COO(M₁) _(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₆ alkyl, C₁-C₆ haloalkyl, C₁ -C₆ hydroxyalkyl, C₁ -C₄ cycloalkyl, C₃ -C₆cycloalkyl, phenyl, benzyl or R₄ -X-; or in which an aromatic orheteroaromatic ring which is unsubstituted or substituted by halogen,--CN, --NO₂, R₆ R₇ R₈ Si--, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2),--SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₁ -C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, phenyl, benzylor R₁₃ -X₁ - is optionally fused onto adjacent carbon atoms;

R₁, R₂ and R₃ independently of one another are C₁ -C₄ alkyl, C₁ -C₄perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal;

R₄ and R₁₃ independently of one another are C₁ -C₆ alkyl, C₁ -C₆haloalkyl, C₁ -C₆ hydroxyalkyl or C₃ -C₆ cycloalkyl;

X and X₁ independently of one another are --O--, --S--, --CO--, --SO--or --SO₂ --;

R₆, R₇ and R₈ independently of one another are C₁ -C₄ alkyl, C₁ -C₄perfluoroalkyl, phenyl or benzyl; and

Q₂ is hydrogen.

The cycloolefin radical of the formula II is particularly preferablyunsubstituted or substituted cyclopropenyl, cyclobutenyl, cyclopentenyl,cycloheptenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl,cycloheptadienyl, cyclooctadienyl and norbornenyl or norbornenylderivatives, such as, for example, 7-oxa-2,2,2-cycloheptene, and thecorresponding benzo derivatives. Substituents are preferably C₁ -C₄alkyl and C₁ -C₄ alkoxy.

Particularly suitable radicals of the formula II are norbornenyl andnorbornenyl derivatives. Particularly preferred compounds from thesenorbornenyl derivatives are those which correspond either to the formulaIII ##STR4## in which X₃ is --CHR₁₆ --, oxygen or sulfur;

R₁₄ and R₁₅ independently of one another are hydrogen, --CN,trifluoromethyl, (CH₃)₃ Si--O--, (CH₃)₃ Si-- or --COOR₁₇ ; and

R₁₆ and R₁₇ independently of one another are hydrogen, C₁ -C₁₂ -alkyl,phenyl or benzyl; or to the formula IV ##STR5## in which X₄ is --CHR₁₉--, oxygen or sulfur;

R₁₉ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl; and

R₁₈ is hydrogen, C₁ -C₆ alkyl or halogen.

The cycloolefin radical of the formula II is particularly preferablynorbornenyl of the formula ##STR6##

In formula I, n is preferably an integer from 2 to 6, particularlypreferably 2 to 4, and especially preferably 2 or 3.

In formula I, B is preferably an n-valent bridging group.

Possible divalent bridging groups are, for example, those of the formulaV

    --X.sub.5 --R.sub.20 --X.sub.6 --                          (V),

in which

X₅ and X₆ independently of one another are a direct bond, --O--, --CH₂--O--, --C(O)O--, --O(O)C--, --CH₂ --O(O)C--, --C(O)--NR₂₁ --, --R₂₁N--(O)C--, --NH--C(O)--NR₂₁ --, --O--C(O) --NH--, --CH₂ --O--C(O)--NH--or --NH--C(O)--O-- and

R₂₀ is C₂ -C₁₈ alkylene, C₅ -C₈ cycloalkylene which is unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, C₆ -C₁₈ arylene or C₇ -C₁₉aralkylene which are unsubstituted or substituted by C₁ -C₄ alkyl or C₁-C₄ alkoxy, or polyoxaalkylene having 2 to 12 oxaalkylene units and 2 to6 C atoms in the alkylene, and

R₂₁ is H or C₁ -C₆ alkyl.

Alkylene R₂₀ preferably contains 2 to 12, and particularly preferably 2to 8 C atoms. The alkylene can be linear or branched. Preferredcycloalkylene is cyclopentylene, and in particular cyclohexylene. Someexamples of arylene are phenylene, naphthylene, biphenylene, biphenyleneether and anthracenylene. An example of aralkylene is benzylene. Thepolyoxaalkylene preferably contains 2 to 6, and particularly preferably2 to 4 units, and preferably 2 or 3 C atoms in the alkylene.

In a preferred embodiment, in formula V

a) X₅ and X₆ are a direct bond and R₂₀ is C₂ -C₁₈ alkylene, preferablyC₂ -C₁₂ alkylene, or

b) X₅ and X₆ are --O--, --CH₂ --O--, --C(O)O--, --O(O)C--, --CH₂--O(O)C--, --C(O)--NR₂₁ --, --O--C(O)--NH-- or --CH₂ --O--C(O)--NH--,and R₂₀ is C₂ --C₁₂ alkylene, phenylene, naphthylene or benzylene whichare unsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or--R₂₂ --(O--R₂₂ --)_(x) --OR₂₂ --, in which x is a number from 2 to 4,and R₂₂ is --C₂ -C₄ alkylene.

Some examples of compounds of the formula I with a divalent bridginggroup are ##STR7##

The compounds of the formula I with a bridging group of the formula Vwhich is a pure hydrocarbon bridge are obtainable, for example, by meansof Diels-Alder reaction of a cyclic diene with a linear or branchedaliphatic diene (see also EP-A-0 287,762), substance mixtures which areeither further used directly or separated beforehand by means ofcustomary methods often being formed. Compounds of the formula I with abridging group of the formula V in which X₅ and X₆ are not a direct bondare obtainable from the corresponding halides or dihalides, alcohols ordiols, amines or diamines, carboxylic acids or dicarboxylic acids orisocyanates or diisocyanates in a manner known per se by etherification,esterification or amidation reactions.

Possible trivalent bridging groups are, for example, those of theformula VI ##STR8## in which X₅, X₆ and X₇ are --O--, --CH₂ --O--,--C(O)O--, --O(O)C--, --CH₂ --O(O)C--, --C(O)--NR₂₁ --, --R₂₁ N--(O)C--,--NH--C(O)--NR₂₁ --, --O--C(O)--NH--, --CH₂ --O--C(O)--NH-- or--NH--C(O)--O--, and

R₂₃ is a trivalent aliphatic hydrocarbon radical having 3 to 20,preferably 3 to 12, C atoms, a trivalent cycloaliphatic radical whichhas 3 to 8, preferably 5 or 6, ring C atoms and is unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or a trivalent aromaticradical which has 6 to 18, preferably 6 to 12, C atoms and isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, atrivalent araliphatic radical which has 7 to 19, preferably 7 to 12, Catoms and is unsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄alkoxy, or a trivalent heteroaromatic radical which has 3 to 13 C atomsand 1 to three heteroatoms from the group consisting of --O--, --N-- and--S-- and is unsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄alkoxy, and

R₂₁ is H or C₁ -C₆ alkyl.

In a preferred embodiment, X₅, X₆ and X₇ are --O--, --CH₂ --, --C(O)O--,--O(O)C--, --CH₂ --O(O)C--, --C(O)--NR₂₁ --, --O--C(O)--NH-- or --CH₂--O--C(O)--NH--.

Preferred radicals R₂₃ are derived, for example, from triols, such asglycerol, trimethylolpropane, butanetriol, pentanetriol, hexanetriol,trihydroxycyclohexane, trihydroxybenzene and cyanuric acid; triamines,such as diethylenetriamine; tricarboxylic acids, such ascyclohexanetricarboxylic acid or trimellitic acid; and triisocyanates,such as benzene triisocyanate or cyanuric triisocyanate.

Some examples of compounds of the formula I with a trivalent bridginggroup are ##STR9##

Possible tetravalent bridging groups are, for example, those of theformula VII ##STR10## in which X₅, X₆, X₇ and X₈ are --C(O)O--, --CH₂--O(O)C-- or --C(O)--NR₂₁ -- and

R₂₄ is a tetravalent aliphatic hydrocarbon radical having 4 to 20,preferably 4 to 12, C atoms, a tetravalent cycloaliphatic radical whichhas 4 to 8, preferably 5 or 6, ring C atoms and is unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or a tetravalent aromaticradical which has 6 to 18, preferably 6 to 12, C atoms and isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, atetravalent araliphatic radical which has 7 to 19, preferably 7 to 12 Catoms and is unsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄alkoxy, or a tetravalent heteroaromatic radical which has 3 to 13 Catoms and 1 to three heteroatoms from the group consisting of --O--,--N-- and --S-- and is unsubstituted or substituted by C₁ -C₄ alkyl orC₁ -C₄ alkoxy, and

R₂₁ is H or C₁ -C₆ alkyl.

Some examples of tetrafunctional compounds from which R₂₄ can be derivedare pentaerythritol, pyromellitic acid and3,4,3',4'-biphenyltetracarboxylic acid.

The same methods as for the preparation of the abovementioned compoundswith a di- or trivalent radical can be used as the preparation methods.

Some examples of compounds of the formula I with a tetravalent bridginggroup are ##STR11##

Polyols, such as dipentaerythritol or hexahydroxyhexane, which can bereacted with corresponding cycloolefinmonocarboxylic acids can bementioned as an example of compounds which are more than tetravalent andfrom which the bridging group can be derived.

In a particularly preferred embodiment of the invention, the compoundsof the formula I contain only carbon and hydrogen atoms, since thepolymers of these are ecologically valuable inasmuch as they can berecycled by simple pyrolysis processes.

The compounds of the formula I are suitable as crosslinking agents inthe thermally induced or radiation-induced polymerization ofolefinically unsaturated compounds. The compounds of the formula I, bythemselves or together with other monomers capable of metathesispolymerization, are outstandingly suitable for the preparation ofcrosslinked metathesis polymers using thermal or photochemicalone-component catalysts.

The invention also relates to a composition of

(a) at least one compound of the formula I

    (A).sub.n --B                                              (I),

in which A is the radical of a strained cycloolefin, B is a direct bondor an n-valent bridging group and n is an integer from 2 to 8, and

(b) a catalytic amount of at least one one-component catalyst formetathesis polymerization which can be activated by heat or radiction,with the exception of norbornenecarboxylic acid norbenenemethyl ester ofthe formula ##STR12## in combination with a catalytic amount of at leastone heat-stable molybdenum(VI) or tungsten(VI) compound which contains,bonded to the metal, at least two methyl groups or two monosubstitutedmethyl groups, the substituent containing no hydrogen atom in the αposition.

The abovementioned preferred meanings apply to A, B and n.

Heat stability in the context of the invention means that thephotocatalytically active metal compounds form no active species forring opening metathesis polymerization on heating. For example, thecatalyst cannot initiate ring-opening metathesis polymerization at roomtemperature up to a slightly elevated temperature, such as about +40°C., within weeks with exclusion of light. During this period only aninsignificant amount of monomer (less than 0.2% by weight) is reacted.The heat stability can be determined, for example, by storing a toluenesolution with 20% by weight of monomer and 0.33% by weight of metalcatalyst at 50° C. for 96 hours in the dark, and any amount of polymerformed, which is evident from the rise in viscosity and can bedetermined quantitatively by precipitation in a precipitant, for exampleethanol, filtration and drying, is not more than 0.5% by weight andpreferably not more than 0.2% by weight.

The compositions according to the invention advantageously comprise thefollowing new thermal and/or photochemical one-component catalysts:

1. Heat-stable ruthenium or osmium compounds which can be activated byradiation and contain at least one photolabile ligand bonded to theruthenium or osmium atom, and whose remaining coordination sites aresatisfied by non-photolabile ligands.

Organic or inorganic compounds, atoms or ions which are coordinated ontoa metal centre are designated as ligands for the ruthenium and osmiumcompounds to be used according to the invention.

Photolabile ligand in the context of the present invention means that,when the catalyst is irradiated by light in the visible or ultravioletrange of the spectrum, the ligand is dissociated from the catalyst and acatalytically active species for the metathesis polymerization isformed. Nonionic photolabile ligands are preferred according to theinvention.

The photolabile ligands can be, for example, nitrogen (N₂), monocyclic,polycyclic or fused arenes which have 6 to 24, preferably 6 to 18, andparticularly preferably 6 to 12 C atoms and are unsubstituted orsubstituted by OH, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₆ -C₁₂ aryl or halogen,or monocyclic heteroarenes, fused heteroarenes or fusedarene-heteroarenes which have 3 to 22, preferably 4 to 16, and inparticular 4 to 10 C atoms and 1 to 3 heteroatoms chosen from the groupconsisting of O, S and N and are unsubstituted or substituted by C₁ -C₄alkyl, C₁ -C₄ alkoxy or halogen; or aliphatic, cycloaliphatic, aromaticor araliphatic nitriles which have 1 to 22, preferably 1 to 18,particularly preferably 1 to 12, and especially preferably 1 to 7 Catoms and are unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄alkoxy or halogen. The preferred substituents are methyl, ethyl,methoxy, ethoxy, fluorine, chlorine and bromine. The arenes andheteroarenes are preferably substituted by one or two radicals andparticularly preferably are unsubstituted. Preferred heteroarenes arethe electron-rich heteroarenes. The arenes and heteroarenes can be bothπ- and σ-bonded; in the latter case, they are then the correspondingaryl and heteroaryl radicals. The aryl preferably contains 6 to 18,particularly preferably 6 to 12 C atoms. The heteroaryl preferablycontains 4 to 16 C atoms.

Some examples of arenes and heteroarenes are benzene, p-cumene,biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene,pyrene, chrysene, fluoranthrene, furan, thiophene, pyrrole, pyridine,γ-pyran, γ-thiopyran, pyrimidine, pyrazine, indole, coumarone,thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole,imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole,quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine,phenothiazine, triazine, thianthrene and purine. Preferred arenes andheteroarenes are benzene, naphthalene, thiophene and benzothiophene. Thearene is especially preferably benzene, and the heteroarene isespecially preferably thiophene.

The nitriles can be substituted, for example by methoxy, ethoxy,fluorine or chlorine; the nitriles are preferably unsubstituted. Thealkylnitriles are preferably linear. Some examples of nitriles areacetonitrile, propionitrile, butyronitrile, pentylnitrile, hexylnitrile,cyclopentyl- and cyclohexylnitrile, benzonitrile, methylbenzonitrile,benzylnitrile and naphthyinitrile. The nitriles are preferably linear C₁-C₄ alkylnitriles or benzonitrile. Of the alkylnitriles, acetonitrile isparticularly preferred.

In a preferred subgroup, the photolabile ligands are N₂, or benzene,thiophene, benzonitrile or acetonitrile which are unsubstituted orsubstituted by one to three C₁ -C₄ alkyl.

Non-photolabile ligand (also called highly coordinating ligand) in thecontext of the present invention means that the ligand does notdissociate, or dissociates to only an insignificant extent, from thecatalyst on irradiation of the catalyst in the visible or nearultraviolet range of the spectrum.

The non-photolabile ligands can be, for example, solvating inorganic andorganic compounds which contain the heteroatoms O, S or N and are oftenalso used as solvents, or cyclopentadienyl or indenyl which areunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, (C₁ -C₄alkyl)₃ Si or (C₁ -C₄ alkyl)₃ SiO--. Examples of such compounds are H₂O, H₂ S, NH₃ ; optionally halogenated, in particular fluorinated orchlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having 1to 18, preferably 1 to 12, and particularly preferably 1 to 6 C atoms,aromatic alcohols or thiols having 6 to 18, preferably 6 to 12 C atoms,araliphatic alcohols or thiols having 7 to 18, preferably 7 to 12 Catoms; aliphatic, cycloaliphatic, araliphatic or aromatic ethers,thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acidesters, lactones, optionally N-C₁ -C₄ mono- or -dialkylated carboxylicacid amides having 2 to 20, preferably 2 to 12, and in particular 2 to 6C atoms, and optionally N-C₁ -C₄ alkylated lactams; aliphatic,cycloaliphatic, araliphatic or aromatic primary, secondary and tertiaryamines having 1 to 20, preferably 1 to 12, and particularly preferably 1to 6 C atoms; and optionally cyclopentadienyls, such as, for example,cyclopentadienyl, indenyl and mono- or polymethylated ortrimethylsilylated cyclopentadienyls or indenyls.

Examples of such non-photolabile ligands are methanol, ethanol, n- andi-propanol, n-, i- and t-butanol, 1,1,1-trifluoroethanol,bistrifluoromethylmethanol, tristrifluoromethylmethanol, pentanol,hexanol, methyl- or ethylmercaptan, cyclopentanol, cyclohexanol,cyclohexylmercaptan, phenol, methylphenol, fluorophenol,phenylmercaptan, benzylmercaptan, benzyl alcohol, diethyl ether,dimethyl ether, diisopropyl ether, di-n- or di-t-butyl ether,tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether,tetrahydrothiophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- andpentamethylene sulfoxide, dimethyl sulfone, diethyl sulfone, tetra- andpentamethylene sulfone, acetone, methyl ethyl ketone, diethyl ketone,phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone,acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde,ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide,pyrrolidone and N-methylpyrrolidone, indenyl, cyclopentadienyl, methyl-or dimethyl- or pentamethylcyclopentadienyl andtrimethylsilylcyclopentadienyl.

The primary amines can correspond to the formula R₂₅ NH₂, the secondaryamines can correspond to the formula R₂₅ R₂₆ NH and the tertiary aminescan correspond to the formula R₂₅ R₂₆ R₂₇ N in which R₂₅ is C₁ -C₁₈alkyl, C₅ - or C₆ cycloalkyl which is unsubstituted or substituted by C₁-C₄ alkyl or C₁ -C₄ alkoxy, or C₆ -C₁₈ aryl or C₇ -C₁₂ aralkyl which areunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, R₂₆independently has the meaning of R₂₅, or R₂₅ and R₂₆ together aretetramethylene, pentamethylene, 3-oxa-1,5-pentylene or --CH₂ --CH₂--NH--CH₂ --CH₂ -- or --CH₂ --CH₂ --N(C₁ -C₄ alkyl) --CH₂ --CH₂ --, R₂₅and R₂₆ independently of one another are as defined above [sic] and R₂₇independently has the meaning of R₂₅. The alkyl preferably contains 1 to12, and particularly preferably 1 to 6 C atoms. The aryl preferablycontains 6 to 12 C atoms and the aralkyl preferably contains 7 to 9 Catoms. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-,diethyl-, triethyl-, methyl-ethyl-, dimethyl-ethyl-, n-propyl-,di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and benzylamine, andpyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine andN-methylmorpholine.

In a preferred subgroup, the non-photolabile ligands are H₂ O, NH₃ andC₁ -C₄ alkanols which are unsubstituted or partly or completelyfluorinated. H₂ O, NH₃, cyclopentadienyl, methanol and ethanol areespecially preferred.

The ruthenium and osmium compounds to be used according to the inventioncan be mono- or polynuclear, for example those with two or metalcentres. The metal atoms here can be bonded via a bridging group ormetal-metal bonds. Preferred compounds with several metal centres arethose of the formula VIII ##STR13## in which Lig is a photolabile ligandand Me is Ru or Os, A₉, A₁₀ and A₁₁ are a bivalent bridging group, andY.sup.⊖ is a monovalent non-coordinating anion. The bridging group ispreferably ionic and particularly preferably a halide, especiallypreferably chloride, bromide or iodide. The photolabile ligand ispreferably identical or different arenes and Y.sup.⊖ can be the anionslisted below, and especially chloride, bromide or iodide. One example ofsuch complexes is [C₆ H₆ Ru(Cl)₃ RuC₆ H₆ ]Cl.

Preferred catalysts according to the invention correspond to the formulaIX

    [(Me.sup.+n)(L.sub.1.sup.z1).sub.m (L.sub.2.sup.z2).sub.o (L.sub.3.sup.z3).sub.p (L.sub.4.sup.z4).sub.q (L.sub.5.sup.z5).sub.r (L.sub.6.sup.z6).sub.s ](L.sub.7.sup.z7).sub.t            (IX)

in which

Me is ruthenium or osmium;

n is 0, 1,2,3,4,5,6,7 or 8;

L₁ is a photolabile ligand;

L₂, L₃, L₄, L₅ and L₆ independently of one another are a non-photolabileor a photolabile ligand;

m is 1, 2, 3, 4, 5, or 6;

o, p, q, r, and s independently of one another are 0, 1, 2, 3, 4 or 5;

z₁, z₂, z₃, Z₄, z₅, z₆ and z₇ independently of one another are -4, -3,-2, -1,0, +1 or +2; and

L₇ is a non-coordinating cation or anion;

the sum of m+o+p+q+r+s being an integer from 2 to 6 and t being thequotient of (n+m·z₁ +o·z₂ +p·z₃ +q·z₄ +r·z₅ +s·z₆)/z₇.

In the formula IX, L₇ is preferably halogen (for example Cl, Br and I),the anion of an oxygen acid, BF₄, PF₆, SiF₆ or AsF₆.

The anions of oxygen acids can be, for example, sulfate, phosphate,perchlorate, perbromate, periodate, antimonate, arsenate, nitrate,carbonate, the anion of a C₁ -C₈ carboxylic acid, such as, for example,formate, acetate, propionate, butyrate, benzoate, phenylacetate ormono-, di- or trichloro- or -fluoroacetate, sulfonates, such as, forexample, methylsulfonate, ethylsulfonate, propylsulfonate,butylsulfonate, trifluoromethylsulfonate (triflate) or phenylsulfonateor benzylsulfonate which are optionally substituted by C₁ -C₄ alkyl, C₁-C₄ alkoxy or halogen, in particular fluorine, chlorine or bromine, suchas, for example, tosylate, mesylate, brosylate, p-methoxy- orp-ethoxyphenylsulfonate, pentafluorophenylsulfonate or2,4,6-triisopropylsulfonate, and phosphonates, such as, for example,methylphosphonate, ethylphosphonate, propylphosphonate,butylphosphonate, phenylphosphonate, p-methylphenylphosphonate orbenzylphosphonate.

In formula IX, Me is preferably ruthenium, in particular Ru²⁺.

A group of compounds of the formula IX which is to be singled out inparticular is that in which the ligands L₁, L₂, L₃, L₄, L₅ and L₆independently of one another are aliphatic, cycloaliphatic, aromatic oraraliphatic nitriles which have 1 to 22 C atoms and are unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen, or C₆ -C₁₈ aryl;or L₁, L₂ and L₃ together are monocyclic, polycyclic or fused areneswhich have 6 to 24, preferably 6 to 18, and particularly preferably 6 to12 C atoms and are unsubstituted or substituted by --OH, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₆ -C₁₂ aryl or halogen, or monocyclic heteroarenes,fused heteroarenes or fused arene-heteroarenes which have 4 to 22 Catoms and 1 to 3 heteroatoms chosen from the group consisting of O, Sand N and are unsubstituted or substituted by --OH, C₁ -C₄ alkyl, C₁ -C₄alkoxy or halogen, and L₄, L₅ and L₆ together have the same meaning, orindividually independently of one another are N₂ or the said nitrile orthe said C₆ -C₁₈ aryl.

A preferred subgroup of the above compounds of the formula IX are thosein which the ligands L₁, L₂, L₃, L₄, L₅ and L₆ independently of oneanother are N₂, C₁ -C₂₀ alkylnitrile C₆ -C₁₂ aryinitrile, C₇ -C₁₂aralkylnitrile or C₆ -C₁₂ aryl, or L₁, L₂ and L₃ in each case to thegroups A₁ or A₂ ##STR14## in which R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄,R₃₅, R₃₆ and R₃₇ independently of one hydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀alkoxy, aryl or SiR₃₈ R₃₉ R₄₀, where, in the groups A₁ and A₂, aromaticor heteroaromatic ring, the heteroatoms of which are chosen from oxygen,sulfur and nitrogen, can be fused onto adjacent carbon atoms; and R₃₈,R₃₉ and R₄₀ independently of one another are C₁ -C₁₂ alkyl, C₅ - or C₆-cycloalkyl, or phenyl or benzyl which are unsubstituted or substitutedby C₁ -C₆ alkyl or C₁ -C₆ alkoxy, preferably C₁ -C₈ alkyl, phenyl orbenzyl, particularly preferably C₁ -C₄ alkyl, phenyl or benzyl, and L₄,L₅ and L₆ likewise together have this meaning, or each individually areN₂, the said nitriles or the said C₆ -C₁₂ aryl, or an arene orheteroarene.

From this group of compounds of the formula IX which are to be singledout, preferred compounds are those in which

L₁, L₂, L₃, L₄, L₅ and L₆ independently of one another are C₁ -C₁₂alkylnitrile or C₆ -C₁₂ aryinitrile, or L₁, L₂ and L₃ in each casetogether are the groups A₁ or A₂ and L₄, L₅ and L₆ likewise togetherhave this meaning or in each case individually are N₂, the said nitrilesor the said arene or heteroarene of the formulae A₁ and A₂, in whichR₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ independently of oneanother are hydrogen, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, SiR₃₈ R₃₉ R₄₀ orphenyl, where, in the groups A₁ and A₂, a benzene ring can be fused ontoadjacent carbon atoms, and R₃₈, R₃₉ and R₄₀ are methyl, ethyl or phenyl.

In an especially preferred embodiment of the process according to theinvention, the catalyst used corresponds to the formula IX in which

L₁, L₂, L₃, L₄, L₅ and L₆ independently of one another aremethylnitrile, ethylnitrile or phenylnitrile, or L₁, L₂ and L₃ in eachcase together are the groups A₁ or A₂ and L₄, L₅ and L₆ likewisetogether have this meaning or in each case individually are the saidnitriles, in which R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇independently hydrogen, methyl, methoxy or phenyl where, in the groupsA₁ and A₂, a benzene ring can be fused onto adjacent carbon atoms.

Another particularly preferred subgroup of the compounds of the formulaIX are those in which L₁, L₂ and L₃ together are monocyclic, polycyclicor fused arenes which have 6 to 24, preferably 6 to 18, and particularlypreferably 6 to 12 C atoms and are unsubstituted or substituted by C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₆ -C₁₂ aryl or halogen, or monocyclicheteroarenes, fused heteroarenes or fused arene-heteroarenes which have4 to 22, preferably 4 to 16, and particularly 4 to 10 C atoms and 1 to 3heteroatoms chosen from the group consisting of O, S and N and areunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen,and L₄, L₅ and L₆ are a non-photolabile ligand, the previous preferredmeanings also applying here.

In this subgroup, L₁, L₂ and L₃ are preferably benzene or naphthalene,and the non-photolabile ligand is preferably H₂ O, NH₃, C₁ -C₄ alkanolor -alkanethiol which is unsubstituted or substituted by fluorine,aliphatic ethers, thioethers, sulfoxides and sulfones having 2 to 8 Catoms, dimethylformamide or N-methylpyrrolidone.

In another preferred subgroup of compounds of the formula X, thecompounds are ruthenium and osmium compounds of the formula X

    [L.sub.1 Me)L.sub.8).sub.5 ].sup.2⊖ [Y.sub.1.sup.x⊖ ].sub.2/x                                                 (X),

in which L₁ is a photolabile ligand and L₈ is a non-photolabile ligand,Me is Ru or Os, Y₁ is a non-coordinating anion and x is the numbers 1, 2or 3. For the photolabile ligands, non-photolabile ligands, Me and Y₁,the abovementioned preferred meanings apply. Particularly preferably, L₁is N₂ or a nitrile, such as, for example, C₁ -C₄ alkylnitrile(acetonitrile), benzonitrile or benzylnitrile, L₈ is NH₃ or an aminehaving 1 to 12 C atoms, Y₁ is a non-coordinating anion and x is thenumber 1 or 2.

Catalysts which are particularly suitable for the present invention are(tos is tosylate and tis is 2,4,6-triisopropylphenylsulfonate): Ru(CH₃CN)₆ (tos)₂, Ru(CH₃ CH₂ CH)₆ (tos)₂, Ru(CH₃ CN)₆ (CF₃ SO₃)₂, Ru(CH₃ CH₂CN)₆ (CF₃ SO₃)₂, Ru(C₆ H₆)₂ (tos)₂, [Ru(C₆ H₆)(C₆ H₅ OCH₃)](BF₄)₂,[Ru(C₆ H₆)(C₆ H₅ i-propyl)](BF₄)₂, [Ru(C₆H₆)(1,3,5-trimethylphenol)](BF₄)₂, [Ru(C₆ H₆)(hexamethylbenzene)](BF₄)₂,[Ru(C₆ H₆)(biphenyl)](BF₄)₂, [Ru(C₆ H₆)(chrysene)](BF₄)₂, [Ru(C₆H₆)(naphthalene)](BF₄)₂, [Ru(cyclopentadienyl)(4-methylcumyl)]PF₆,[Ru(cyanophenyl)₆ ](tos)₂, [Ru(cyanophenyl)₆ ](CF₃ SO₃)₂, [Ru(C₆H₆)(tetramethylthiophene)₃ ](tos)₂, [Ru(C₆ H₆)(CH₃ CN)₃ ](tos)₂, [Ru(C₆H₆)(tetramethylthiophene)₃ ](CF₃ SO₃)₂, [Ru(C₆ H₆)(CH₃ CN)3](CF₃ SO₃)₂,[Ru(C₆ H₆)(CH₃ OH)₃ ](tos)₂, [Ru(C₆ H₆)(CH₃ OH)₃ ](tis)₂, [Os(NH₃)₅ N₂](PF₆)₂, [Ru(NH₃)₅ N₂ ](PF₆)₂, [Ru(NH₃)₅ (CH₃ CN)]BF₄, [Ru(C₆ H₆ (NH₃)₃](tis)₂, [Ru(C₆ H₆ (tetrahydrothiophene)₃ ](CF₃ SO₃)₂, [Ru((CH₃)₂ S)₃ C₆H₆ ](tos)₂, [Ru(dimethyl sulfoxide)₃ C₆ H₆ ](PF₆)₂,[Ru(dimethylformamide)₃ C₆ H₆ ](PF₆)₂, [Ru(C₆ H₆)Cl₂ ]₂ and [Os(C₆H₆)Cl₂ ]₂.

Ruthenium and osmium catalysts to be used according to the invention areeither known and in some cases commercially obtainable, or can beprepared analogously to known processes. Such catalysts and theirpreparation are described, for example, in Gilkerson, W. R., Jackson, M.D., J. Am. Chem. Soc. 101:4096-411 (1979), Bennett, M. A., Matheson, T.W., J. Organomet. Chem. 175:87-93 (1979), Moorehouse, S., Wilkinson, G.,J. Chem. Soc.; Dalton Trans., 2187-2190 (1974) and Luo, S., Rauchfuss,T. B., Wilson, S. R., J. Am. Chem. Soc. 114:8515-8520 (1992).

2. Heat-stable molybdenum(VI) or tungsten(VI) compounds which can beactivated thermally or with radiation and contain, bonded to the metal,at least two methyl groups or two monosubstituted methyl groups, thesubstituent containing no hydrogen atom in the α position.

The other valencies of the molybdenum and tungsten are preferablysatisfied by heat-stable neutral ligands, a large number of which areknown. The number of neutral ligands can exceed the stoichiometricallypossible number (solvates). Heat stability has been explained above. Attemperatures above 50° C., for example 60 to 300° C., these molybdenumand tungsten compounds can also be activated thermally.

The molybdenum and tungsten compounds to be used according to theinvention can be those which contain one metal atom, or two metal atomswhich are bonded via a single, double or triple bond. The methyl groupor monosubstituted methyl group which is bonded to the metal is bondedat least twice, particularly preferably two to six times, and especiallypreferably two to four times, as a ligand. The other valencies of themolybdenum and tungsten are preferably satisfied by heat-stable neutralligands, the definition of heat stability having been given above. Thisligand preferably corresponds to the formula XI

    --CH.sub.2 --R                                             (XI),

in which R is H, --CF₃, --SiR₃₈ R₃₉ R₄₀, --CR₄₁ R₄₂ R₄₃, C₆ -C₁₆ arylwhich is unsubstituted or substituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxyor C₄ -C₁₅ heteroaryl having 1 to 3 heteroatoms from the groupconsisting of O, S and N; and

R₄₁, R₄₂ and R₄₃ independently of one another are C₁ -C₁₀ alkyl, whichis unsubstituted or substituted by C₁ -C₁₀ alkoxy, or R₄₁ and R₄₂ havethis meaning and R₄₃ is C₆ -C₁₀ aryl or C₄ -C₉ heteroaryl, which isunsubstituted or substituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy; and

R₃₈, R₃₉ and R₄₀ have the abovementioned meanings.

Alkyl R₃₈ to R₄₃ can be linear or branched and can preferably contain 1to 8 and particularly preferably 1 to 4 C atoms. Aryl R₃₈ to R₄₃ ispreferably phenyl or naphthyl.

Aryl R in formula XI is preferably phenyl or naphthyl.

Heteroaryl R in formula XI is preferably pyridinyl, furanyl, thiophenylor pyrrolyl.

Preferred substituents for R₃₈ to R₄₃ in the context of the definitionsare methyl, ethyl, methoxy and ethoxy. Examples of the radicals R₃₈ toR₄₃ have been given above under the compounds of the formula I.

In a preferred embodiment, the group R in formula XI is H, --C(CH₃)₃,--C(CH₃)₂ C₆ H₅, phenyl which is unsubstituted or substituted by methyl,ethyl, methoxy or ethoxy, --CF₃ or --Si(CH₃)₃.

The other valencies of the Mo(VI) and W(VI) atoms are optionallysatisfied with identical or different ligands from the group consistingof ═O, ═N--R₄₄, secondary amines having 2 to 18 C atoms, R₄₅ O--, R₄₅S--, halogen, optionally substituted cyclopentadienyl, bridgedbiscyclopentadienyl, tridentate monoanionic ligands and neutral ligands,such as, for example, ethers, nitriles, CO and tertiary phosphines andamines, in which the R₄₅ independently of one another are linear orbranched C₁ -C₁₈ alkyl which is unsubstituted or substituted by C₁ -C₆alkoxy or halogen, C₅ - or C₆ cycloalkyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen, phenyl which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen, or benzyl or phenylethylwhich are unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy,C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen; and R₄₄ is linear orbranched C₁ -C₁₈ alkyl which is unsubstituted or substituted by C₁ -C₆alkoxy, C₅ - or C₆ cycloalkyl which is unsubstituted or substituted byC₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen, phenyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆alkoxyethyl, di(C₁ -C₆ alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkylor halogen, or benzyl or phenylethyl which are unsubstituted orsubstitued by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆alkoxyethyl or halogen.

Secondary amines are preferably those of the formula R₄₆ R₄₇ N--, inwhich R₄₆ and R₄₇ independently of one another are linear or branched C₁-C₁₈ alkyl; C₅ - or C₆ cycloalkyl; benzyl or phenylethyl which areunsubstituted or substituted by C₁ -C₆ alkoxy or halogen, or (C₁ -C₆alkyl)₃ Si; or R₄₆ and R₄₇ together are tetramethylene, pentamethyleneor 3-oxapentane-1,5-diyl. The alkyl preferably contains 1 to 12, andparticularly preferably 1 to 6 C atoms. Some examples are dimethyl-,diethyl-, di-n-propyl-, di-i-propyl-, di-n-butyl-, methyl-ethyl-,dibenzyl-, benzyl-methyl-, diphenyl- and phenyl-methylamino anddi(trimethylsilyl)amino.

Halogen as a ligand or a substituent is preferably F or Cl andparticularly preferably Cl.

The cyclopentadienyl can be unsubstituted or substituted by one to fiveC₁ -C₄ alkyl, in particular methyl or --Si(C₁ -C₄ alkyl) [sic], inparticular Si(CH₃)₃. Bridged cyclopentadienyls are, in particular, thoseof the formula R₄₈ --A--R₄₈, in which R₄₈ is cyclopentadienyl which isunsubstituted or substituted by one to five C₁ -C₄ alkyl, in particularmethyl or --Si(C₁ -C₄ alkyl) [sic], in particular --Si(CH₃)₃, and A is--CH₂ --, --CH₂ --CH₂ --, --Si(CH₃)₂ --, --Si(CH₃)₃)₂ --Si(CH₃)₂ -- or--Si(CH₃)₂ --O--Si(CH₃)₂ --.

Ethers as neutral ligands can be dialkyl ethers having 2 to 8 C atoms orcyclic ethers having 5 or 6 ring members. Some examples are diethylether, methyl ethyl ether, diethyl ether, di- n-propyl ether,di-i-propyl ether, di-n-butyl ether, ethylene glycol dimethyl ether,tetrahydroforan [sic] and dioxane.

Nitriles as neutral ligands can be aliphatic or aromatic nitriles having1 to 12, preferably 1 to 8 C atoms. Some examples are acetonitrile,propionitrile, butylnitrile, benzonitrile and benzylnitrile.

Tertiary amines and phosphines as neutral ligands can be those having 3to 24, preferably 3 to 18 C atoms. Some examples are trimethylamine and-phosphine, triethylamine and -phosphine, tri-n-propylamine and-phosphine, tri-n-butylamine and -phosphine, triphenylamine and-phosphine, tricyclohexylamine and -phosphine, phenyidimethylamine and-phosphine, benzyldimethylamine and -phosphine and 3,5-dimethylphenyl-dimethylamine and -phosphine.

The tridentate monoanionic ligands can be, for example,hydro(trispyrazol-1-yl)borates or alkyl(trispyrazol-1-yl)borates, whichare unsubstituted or substituted by one to three C₁ -C₄ alkyl [cf.Trofimenko, S., Chem. Rev., 93:943-980 (1993)], or [C₅ (R'₅)Co(R₅₀ R₅₁P═O)₃ ].sup.⊖, in which R' is H or methyl and R₅₀ and R₅₁ independentlyof one another are C₁ -C₄ alkyl, C₁ -C₄ alkoxy or phenyl [cf. Klaui, W.,Angew. Chem. 102:661-670 (1990)].

Halogen as a substituent for the radicals R₄₄ and R₄₅ is preferablyfluorine, and particularly preferably chlorine. The substituents alkyl,alkoxy or alkoxy in alkoxymethyl or -ethyl preferably contain 1 to 4,and in particular 1 or 2 C atoms. Examples are methyl, ethyl, n- andi-propyl, n-, i- and t-butyl, methoxy, ethoxy, n- and i-propyloxy andn-, i- and t-butyloxy.

Alkyl R₄₄ and R₄₅ preferably contain 1 to 12, particularly preferably 1to 8, and especially preferably 1 to 4 C atoms. Alkyl is preferablybranched alkyl. Some examples of R₄₄ are methoxy, ethoxy, n- andi-propyloxy, n-, i- and t-butyloxy, hexafluoro-i-propyloxy and hexa- andperfluorobutyloxy.

Some examples of substituted phenyl and benzyl R₄₄ and R₄₅ arep-methylphenyl or benzyl [sic], p-fluoro- or p-chlorophenyl or -benzyl,p-ethylphenyl or -benzyl, p-n- or i-propylphenyl or -benzyl,p-i-butylphenyl or -benzyl, 3-methyl-phenyl or -benzyl, 3-i-propylphenylor -benzyl, 2,6-dimethylphenyl or -benzyl, 2,6-di-i-propylphenyl or-benzyl, 2,6-di-n- or -t-butylphenyl and -benzyl. R₄₅ is particularlypreferably phenyl which is unsubstituted or substituted by C₁ -C₄ alkylor C₁ -C₄ alkoxy.

In a preferred embodiment, the molybdenum and tungsten compoundscorrespond, in particular, to one of the formulae XII to XIIc ##STR15##in which Me is Mo(VI) or W(VI);

at least two, preferably 2 to 4, of the radicals R₅₃ to R₅₈ are aradical --CH₂ --R of the formula XI, in which R has the abovementionedmeanings;

in each case two of the other radicals of R₅₃ to R₅₈ are ═O or ═N--R₄₄,and R₄₄ has the abovementioned meanings; and/or

the other radicals from R₅₃ to R₅₈ are secondary amino having 2 to 18 Catoms, R₄₅ O-- or R₄₅ S--, halogen, cyclopentadienyl or bridgedbiscyclopentadienyl or a neutral ligand, in which R₄₅ has theabovementioned meanings. The preferred meanings given above apply to theradicals R and R₃₈ to R₄₅.

In a particularly preferred embodiment, molybdenum and tungstencompounds of the formula XII which are used in the composition accordingto the invention are those in which

a) R₅₃ to R₅₈ are a radical of the formula XI --CH₂ --R, or

b) R₅₃ and R₅₄ are a radical of the formula XI --CH₂ --R, R₅₅ and R₅₆together are the radical ═N--R₄₄, and R₅₇ and R₅₈ together independentlyof one another are R₄₅ --O-- or halogen, or

c) R₅₃ and R₅₄ together and R₅₅ and R₅₆ together are the radical═N--R₄₄, and R₅₇ and R₅₈ are a radical of the formula XI --CH₂ --R,

where R, R₄₄ and R₄₅ have the above meanings. The above preferredmeanings apply to R, R₄₄ and R₄₅.

Particularly preferred compounds of the formula XIIc are those in whichR₅₃, R₅₄ and R₅₅ are a radical of the formula XI, the radical of theformula XI particularly preferably being --CH₂ --Si(C₁ -C₄ alkyl)₃.

Molybdenum or tungsten compounds which are especially preferably used inthe composition according to the invention are those of the formulaeXIII, XIIIa or XIIIb ##STR16## in which Me is Mo(VI) or W(VI),

R is H, --C(CH₃)₃, --C(CH₃)₂ --C₆ H₅, --C₆ H₅ or --Si(C₁ -C₄ alkyl)₃,

R₆₃ is phenyl or phenyl which is substituted by 1 to 3 C₁ -C₄ alkyl orC₁ -C₄ alkoxy,

R₅₃ is linear or branched C₁ -C₄ alkoxy which is unsubstituted orsubstituted by fluorine and

R₅₄ has the same meaning as R₅₃ or is F, Cl or Br. R₅₃ is particularlypreferably branched alkoxy, which is optionally partly or completelysubstituted by F, for example i-propyloxy, i- and t-butyloxy,hexafluoropopyloxy [sic] and nonafluoropropyloxy. R₅₄ is preferably Cl.

Some examples of molybdenum and tungsten compounds are:

W(═N--C₆ H₅)(OC(CH₃)₃)(Cl)[(CH₂ Si(CH₃)₃)]₂, [(CH₃)₃ SiCH₂ ]₃Mo.tbd.Mo[CH₂ Si(CH₃)₃ ]₃,

W(═N--C₆ H₅)(OC(CF₃)₂ CH₃)₂ [(CH₂ Si(CH₃)₃)]₂, W(═NC₆ H₅)[CH₂ Si(CH₃)₃]₃ Cl,

Mo(═N--2,6-dimethylC₆ H5)₂ [(CH₂ -C₆ H₅)]₂, W[2,6--(CH₃)₂ C₆ H₃ N]₂ (CH₂-C₆ H₅)₂,

Mo(═N--2,6-diisopropylC₆ H₃)₂ [(CH₂ -C₆ H₅)]₂,

Mo(═N--2,6-diisopropylC₆ H₃)₂ [(CH₂ C(CH₃)₂ --C₆ H₅)]₂ and

Mo(═N--2,6-dimethylC₆ H₃)₂ (CH₃)₂ (tetrahydrofuran)

The molybdenum and tungsten catalysts to be used according to theinvention are known or can be prepared by known and analogous processesstarting from the metal halides by means of Grignard reactions [see, forexample, Huq, F., Mowat, W., Shortland, A., Skapski, A. C., Wilkinson,G., J. Chem. Soc., Chem. Commun. 1079-1080 (1971) or Schrock, R. R.,Murdzeck, J. S., Bazan, G. C., Robbins, J., DiMare, M., O'Regan, M., J.Am. Chem. Soc., 112:3875-3886 (1990)].

3. Heat-stable titanium(IV), niobium(V), tantalum(V), molybdenum(VI) ortungsten(VI) compounds in which a silylmethyl group and at least onehalogen are bound to the metal. These one-component catalysts areparticularly photocatalytically active.

The titanium(IV), niobium(V) and tantalum(V) compounds to be usedaccording to the invention are those which contain one metal atom. Themolybdenum(VI) and tungsten(VI) compounds to be used according to theinvention can be those which contain one metal atom, or two metal atomswhich are bonded via a single, double or triple bond. The othervalencies of the titanium, niobium, tantalum, molybdenum and tungstenare preferably satisfied with heat-stable neutral ligands, thedefinition of heat stability having been given above. The halogen boundto the metal atom is preferably F, Cl, Br and I, more preferably F, Cland Br, and particularly preferably F or Cl. The silylmethyl ligandpreferably corresponds to the formula XIV

    --CH.sub.2 --SiR.sub.38 R.sub.39 R.sub.40                  (XIV),

in which

R₃₈, R₃₉ and R₄₀ independently of one another are C₁ -C₁₈ -alkyl, C₅ -or C₆ cycloalkyl or phenyl or benzyl which are unsubstituted orsubstituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy.

Alkyl R₃₈ to R₄₀ can be linear or branched and can preferably contain 1to 12, particularly preferably 1 to 8, and in particular 1 to 4 C atoms.Methyl and ethyl are the particularly preferred alkyl.

Preferred substituents for phenyl and benzyl R₃₈ to R₄₀ in the contextof the definitions are methyl, ethyl, methoxy and ethoxy.

In a preferred embodiment, R₃₈ to R₄₀ in the group of the formula XIVare C₁ -C₄ alkyl, phenyl or benzyl.

Some examples of the group of the formula XIV are --CH₂ --Si(CH₃)₃,--CH₂ --Si(C₂ H₅)₃, --CH₂ --Si(n--C₃ H₇)₃, --CH₂ --Si(n--C₄ H₉)₃, --CH₂--Si(CH₃)₂ (n--C₄ H₉), --CH₂ --Si(CH₃)₂ (t--C₄ H₉), --CH₂ --Si(CH₃)₂ (C₂H₅), --CH₂ --Si(CH₃)₂ [C(CH₃)₂ CH(CH₃)₂, --CH₂ --Si(CH₃)₂ (n--C₁₂ H₂₅),--CH₂ --Si(CH₃)₂ (n--C₁₈ H₃₇), --CH₂ --Si(C₆ H₅)₃, --CH₂ --Si(CH₂ -C₆H₅)₃, --CH₂ --Si₂ --Si(--C₆ H₅)(CH₃)₂ and --CH₂ --Si(CH₂ -C₆ H₅)(CH₃)₂.--CH₂ --Si(CH₃)₃ is especially preferred.

The other valencies of the Ti(IV), Nb(V), Ta(V), Mo(VI) and W(VI) atomsare optionally satisfied by identical or different neutral ligands, forexample selected from the group consisting of ═O, ═N--R₄₄, secondaryamines having 2 to 18 C atoms, R₄₅ O--, R₄₅ S--, halogen, optionallysubstituted cyclopentadienyl, bridged biscyclopentadienyl, tridentatemonoanionic ligands and neutral ligands, such as, for example, ethers,nitriles, CO and tertiary phosphines and amines, in which the R₄₅independently of one another are linear or branched C₁ -C₁₈ alkyl whichis unsubstituted or substituted by C₁ -C₆ alkoxy or halogen, C5- or C₆cycloalkyl which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl orhalogen, or benzyl or phenylethyl which are unsubstituted or substitutedby C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethylor halogen, with the proviso that in the case of the titanium compounds,the ligand is not ═O or ═N--R₄₄. linear or branched C₁ -C,₈ alkyl whichis unsubstituted or substituted by C₁ -C₆ alkoxy, C₅ -- or C₆ cycloalkylwhich is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy orhalogen, phenyl which is unsubstituted or substituted by C₁ -C₆ alkyl,C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen, or benzyl orphenylethyl which are unsubstituted or substituted by C₁ -C₆ alkyl, C₁-C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen, with theproviso that in the case of the

The meanings and preferred meanings of R₄₄ and R₄₅, of secondary amines,of halogen as a further ligand on the metal atoms or as a substituent,of cyclopentadienyl, ethers, nitriles, tertiary amines and phosphines asneutral ligands and of tridentate monoanionic ligands have been givenabove. The meanings and preferred meanings of alkyl, alkoxy or alkoxy asa substituent in alkoxymethyl or -ethyl have likewise been given above.In a preferred embodiment, the metal compounds correspond, inparticular, to the formulae XV, XVa or XVb ##STR17## in which Me₁ isMo(VI) or W(VI);

Me₂ is Nb(V) or Ta(V);

one of the radicals R₆₉ to R₇₄ is a radical --CH₂ --SiR₃₈ R₃₉ R₄₀ of theformula XIV;

at least one of the radicals R₆₉ to R₇₄ is F, Cl or Br;

R₃₈, R₃₉ and R₄₀ independently of one another are C₁ -C₆ alkyl, C₅ - orC₆ cycloalkyl, or phenyl or benzyl which are unsubstituted orsubstituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy;

in formula XV two or in each case two and in formula XVa two of theother radicals of R₆₉ to R₇₄ each together are ═O or ═N--R₄₄, and R₄₄ islinear or branched C₁ -Cl₈ alkyl which is unsubstituted or substitutedby C₁ -C₆ alkoxy, C₅ - or C₆ cycloalkyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen, phenyl which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆ alkyl)amino, di(C₁ -C₆alkyl)amino-C₁ -C₃ alkyl or halogen, or benzyl or phenylethyl which areunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆ alkyl)amino, di(C₁ -C₆alkyl)amino-C₁ -C₃ alkyl or halogen, and the other radicals aresecondary amino having 2 to 18 C atoms, R₄₅ O-- or R₄₅ S--, halogen,unsubstituted or substituted cyclopentadienyl or bridgedbiscyclopentadienyl or a neutral ligand, in which the R₄₅ independentlyof one another are linear or branched C₁ -C₁₈ alkyl which isunsubstituted or substituted by C₁ -C₆ alkoxy or halogen, C₅ - or C₆cycloalkyl which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁-C₆ alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen, orbenzyl or phenylethyl which are unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen; or

in the formulae XV, XVa and XVb the other radicals independently of oneanother are secondary amino having 2 to 18 C atoms, R₄₅ O-- or R₄₅ S--,halogen, unsubstituted or substituted cyclopentadienyl or bridgedbiscyclopentadienyl or a neutral ligand in which the R₄₅ independentlyof one another are linear or branched C₁ -C,₈ alkyl which isunsubstituted or substituted by C₁ -C₆ alkoxy or halogen, C₅ - or C₆cycloalkyl which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, C₁-C₆ alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen, orbenzyl or phenylethyl which are unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen.

The preferred meanings given above apply to the radicals R₆₉ to R₇₃.

In a particularly preferred embodiment, metal compounds which are usedin the process according to the invention are those of the formulae XV,XVa or XVb in which R₆₉ is a radical of the formula XIV --CH₂ SiR₃₈ R₃₉R₄₀ and R₇₀ is F, Cl or Br; and

(a) in formula XV R₇₁ and R₇₂, and R₇₃ and R₇₄, in each case together,are the radical ═N--R₄₄, or R₇₁ and R₇₂ together are the radical ═N--R₄₄and R₇₃ and R₇₄ independently of one another are unsubstituted orsubstituted cyclopentadienyl, R₄₅ --O-- or halogen, or

(b) in formula XVa R₇, and R₇₂ together are the radical ═N--R₄₄, and R₄₄is unsubstituted or substituted cyclopentadienyl, R₄₅ --O-- or halogen,or in formula XVa R₇₁, R₇₂ and R₇₃ independently of one another areunsubstituted or substituted cyclopentadienyl, R₄₅ --O-- or halogen, or

(c) in formula XVb R₇₁ and R₇₂ independently of one another areunsubstituted or substituted cyclopentadienyl, R₄₅ --O-- or halogen,

where R₃₈ to R₄₄ have the above meanings. The above preferred meaningsapply to R₃₈, R₃₉, R₄₀, R₄₄ and R₄₅.

Metal compounds which are especially preferably used in the processaccording to the invention are those of the formulae XVI, XVIa, XVIb,XVIc or XVId ##STR18## in which Me₁ is Mo(VI) or W(VI);

Me₂ is Nb(V) or Ta(V);

R₇₅ is --Si(C₁ -C₄ alkyl)₃ ;

Z is Cl or Br;

R₆₃ is phenyl or phenyl which is substituted by 1 to 3 C₁ -C₄ alkyl orC₁ -C₄ alkoxy,

(a) R₇₃ and R₇₄ in formula XVI together are the group --NR₆₃ orindividually independently of one another are F, Cl, Br, linear orbranched C₁ -C₄ alkoxy which is unsubstituted or substituted byfluorine, phenyloxy which is unsubstituted or substituted by C₁ -C₄alkyl or C₁ -C₄ alkoxy, or cyclopentadienyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl;

(b) R₇₁, R₇₂, R₇₃ and R₇₄ in formula XVIa independently of one anotherare F, Cl, Br, linear or, in particular, branched C₁ -C₄ alkoxy which isunsubstituted or substituted by fluorine, phenyloxy which isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, orcyclopentadienyl which is unsubstituted or substituted by C₁ -C₄ alkyl;

(c) R₇₃ in formula XVIb is F, Cl, Br, linear or branched C₁ -C₄ alkoxywhich is unsubstituted or substituted by fluorine, phenyloxy which isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, orcyclopentadienyl which is unsubstituted or substituted by C₁ -C₄ alkyl;

(d) R₇₁, R₇₂ and R₇₃ in formula XVIc independently of one another are F,Cl, Br, linear or, in particular, branched C₁ -C₄ alkoxy which isunsubstituted or substituted by fluorine, phenyloxy which isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, orcyclopentadienyl which is unsubstituted or substituted by C₁ -C₄ alkyl;and

(e) R₇₁ and R₇₂ in formula XVId independently of one another are F, Cl,Br, linear or, in particular, branched C₁ -C₄ alkoxy which isunsubstituted or substituted by fluorine, phenyloxy which isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, orcyclopentadienyl which is unsubstituted or substituted by C₁ -C₄ alkyl.The alkoxy is particularly preferably branched alkoxy which isoptionally partly or completely substituted by F, for examplei-propyloxy, i- and t-butyloxy, hexafluoropopyloxy [sic] andnonafluoropropyloxy. The phenyloxy radical is, in particular, phenyloxywhich is substituted by C₁ -C₄ alkyl in the 2,6-positions, for example2,6-dimethylphenyloxy. Examples of substituted cyclopentadienyl radicalsare mono- to pentamethylcyclopentadienyl andtrimethylsilylcyclopentadienyl. R₆₃ is preferably phenyl or phenyl whichis substituted by C₁ -C₄ alkyl, in particular phenyl or 3,5-dimethyl-,2,6-dimethyl-, 3,5-diethyl- and 2,6-diethylphenyl.

Especially preferred compounds in the process according to the inventionare those of the formulae XVII, XVIIa, XVIIb, XVIIc and XVIId ##STR19##in which Me, is Mo(VI) or W(VI);

Me₂ is Nb(V) or Ta(V);

X_(a) is F or Cl;

R₆₃ is phenyl or phenyl which is substituted by 1 or 2 C₁ -C₄ alkylgroups;

R₆₂ is branched C₃ - or C₄ alkyl which is optionally partly orcompletely substituted by fluorine, or phenyloxy, or phenyloxy which issubstituted by 1 to 3 methyl or ethyl groups;

R₇₂ and R₇₃ independently of one another are cyclopentadienyl which isunsubstituted or substituted by 1 to 5 methyl groups, X_(a) or R₆₂ O--;and

R₇₁ is cyclopentadienyl which is unsubstituted or substituted by 1 to 5methyl groups, X_(a) or R₇₂ O--.

Some examples of titanium(IV), niobium(V), tantalum(V), molybdenum(VI)and tungsten(VI) compounds are [Cp is cyclopentadienyl and Me is Nb(V)or Ta(V)]: Ti[CH₂ Si(CH₃)₃ ]Cl₃, Ti[CH₂ Si(CH₃)₃ ]Br₃, Cp₂ Ti[CH₂Si(CH₃)₃ ]Cl, (CH₃)₂ Ti[CH₂ Si(CH₃)₃ ]Cl, Cp₂ Ti[CH₂ Si(CH₃)₃ ]Br, Cp₂Ti[CH₂ Si(Ch₃)₃ ]I CpTi[CH₂ Si(CH₃)₃ ][CH₃ ]Cl, CpTi[CH₂ Si(CH₃)₃ ]Br₂,[(CH₃)₂ CHO]₂ Ti[CH₂ Si(CH₃)₃ ]Cl, [(CF₃)₂ CHO]₂ Ti[CH₂ Si(CH₃)₃ ]Cl,[(CF₃)₂ CHO]CpTi[CH₂ Si(CH₃)₃ ]Cl, [(CH₃)₂ CHO]CpTi[CH₂ Si(CH₃)₃ ]Cl,(C₆ H₅ O)CpTi[CH₂ Si(CH₃)₃ ]Cl, (2,6-dimethyl-C₆ H₅ O)CpTi[CH₂ Si(CH₃)₃]Cl, (2,6-dimethyl-C₆ H₅ O)₂ Ti[CH₂ Si(CH₃)₃ ]Cl, (2,6-dimethyl-C₆ H₅O)Ti[CH₂ Si(CH₃)₃ ]₂ Br, [(CH₃)₃ CO]CpTi[CH₂ Si(CH₃)₃ ]Cl [(CF₃)₂(CH₃)CO]CpTi[CH₂ Si(CH₃)₃ ]Cl, Me(═N--C₆ H₅)[OCH(CH₃)₂ ][CH₂ Si(CH₃)₃]Cl, Cp₂ Me[(CH₂ Si(CH₃)₃ Cl₂, Me(═N--C₆ H₅)[OCH(CF₃)₂ ][(CH₂ Si(CH₃)₃]Cl, Me(═N-2,6-diisopropylC₆ H₃)[(CH₂ Si(CH₃)₃ ]Cl₂,Me(═N-2,6-diisopropylC₆ H₃)[(CH₃)₂ CHO][(CH₂ Si(CH₃)₃ ]Cl,Me(═N-2,6-dimethylC₆ H₃)(2,6-dimethyl-C₆ H₅ O)[CH₂ Si(CH₃)₃ ]Cl,Me(═N-2,6-dimethylC₆ H₃)((CF₃)₂ CHO)[CH₂ Si(CH₃)₃ ]Cl,(═N-2,6-dimethylC₆ H₃)CpMe[(CH₂ Si(CH₃)₃ ]Cl, (C₆ H₅ O)₂ CpMe[(CH₂Si(CH₃)₃ ]Cl, (═N-3,5-dimethylC₆ H₃)Me[2,6-dimethylC₆ H₃ O)][(CH₂Si(CH₃)₃)]Cl, CpMe[OCH(CH₃)₂ ]₂ [(CH₂ Si(CH₃)₃ ]Br, CpMe[OCH(CH₃)₂ ]₂[(CH₂ Si(CH₃)₃ ]Cl, CpMe[OCH(CF₃)₂ ]₂ [(CH₂ Si(CH₃)₃ ]Cl, Cp₂Me(Methyl)[(CH₂ Si(CH₃)₃ ]Cl, Cp₂ Me[OCH(CH₃)₂ ][(CH₂ Si(CH₃)₃ ]Cl,[OCH(CH₃)₂ ]₂ Me[CH₂ Si(CH₃)₃ ]Cl₂, Me(2,6-dimethylphenyloxy)(CH₃ O)₂[(CH₂ Si(CH₃)₃ ]Cl, Me[CH₂ Si(CH₃)₃ ][OCH(CH₃)](CF₃ O)₂ Cl, W(═N--C₆H₅)[(OC(CH₃)₃ ][CH₂ --Si(CH₃)₃ ]Cl₂, (2,6-diisopropylphenyloxY)₂ Me[CH₂Si(CH₃)₃ ]Cl₂, Cp₂ Me[OC(CH₃)₃ ][(CH₂ Si(CH₃)₃ ]Cl, CpMe[OC(CH₃)(CF₃)₂]₂ [(CH₂ Si(CH₃)₃ ]Cl, Mo₂ [(CH₂ --Si(CH₃)₃)(OCH₂ C(CH₃)₃)Cl]₂,Mo(═N-2,6-diisopropylC₆ H₃)2]CH₂ --Si(CH₃)₃ ]Cl, W(═N--C₆ H₅)[(OC(CH₃)₃]₂ [CH₂ --Si(CH₃)₃ ]Cl, Mo(═N--C₆ H₅)₂ [CH₂ --Si(CH₃)₃ ]Cl,Mo(═N-2,6-diisopropylc₆ H₃)[(OCH₂ C(CH₃)₃ ]₂ [CH₂ --Si(CH₃)₃ CL.

The titanium, niobium, tantalum, molybdenum and tungsten compounds to beused according to the invention are known or can be prepared by knownand analogous processes starting from optionally correspondinglysubstituted metal halides by means of Grignard reactions [Schrock, R.R., Murdzeck, J. S., Bazan, G. C., Robbins, J., DiMare, M., O'Regan, M.,J. Am. Chem. Soc., 112:3875-3886 (1990)].

4. Other suitable photoactive one-component catalysts are niobium(V) ortantalum(V) compounds which contain at least two methyl groups or twomonosubstituted methyl groups bonded to the metal, the substituentcontaining no hydrogen atom in the a position. These compounds are alsothermal catalysts.

The niobium(V) and tantalum(V) compounds to be used according to theinvention contain one metal atom. The methyl group or monosubstitutedmethyl group which is bonded to the metal is bonded at least twice,particularly preferably two to five times, and especially preferably twoor three times, as a ligand. This ligand preferably corresponds to theformula XI

    --CH.sub.2 --R                                             (XI)

where R has the meanings and preferred meanings given above.

The other valencies of the niobum and tantalum atom are preferablysatisfied with heat stable neutral ligands, a large number of which areknown. The number of neutral ligands can also exceed thestoichiometrically possible number (solvates). The definition of heatstability has been given in the introduction.

The meanings and preferred meanings of neutral ligands have been givenabove.

In a preferred embodiment, the niobium and tantalum compoundscorrespond, in particular, to the formula XVIII ##STR20## in which Me isNb(V) or Ta(V),

at least two, preferably 2 or 3, of the radicals R₈₂ to R₈₆ are aradical --CH₂ --R of the formula XI, in which R has the meanings andpreferred meanings given above, two of the other radicals from R₈₂ toR₈₆ together are ═O or ═N--R₄₄, and R₄₄ is linear or branched C₁ -Cl₈alkyl which is unsubstituted or substituted by C₁ -C₆ alkoxy, C₅ - or C₆cycloalkyl which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁-C₆ alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen, orbenzyl or phenylethyl which are unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen; and/or

the other radicals from R₈₂ to R₈₆ independently of one another aresecondary amino having 2 to 18 C atoms, R₄₅ O--, R₄₅ S--, halogen,cyclopentadienyl or bridged biscyclopentadienyl or a neutral ligand, inwhich the R₄₅ independently of one another are linear or branched C₁-C₁₈ alkyl which is unsubstituted or substituted by C₁ -Cealkoxy orhalogen, C₅ - or C₆ cycloalkyl which is unsubstituted or substituted byC₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen, phenyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆alkoxyethyl, di(C₁ -C₆ alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkylor halogen, or benzyl or phenyethyl which are unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆alkoxyethyl, di(C₁ -C₆ alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkylor halogen.

In a particularly preferred embodiment, the niobium and tantalumcompounds of the formula XVIII used are those in which

a) R₈₂ to R₈₆ are each a radical of the formula XI --CH₂ --R, or

b) R₈₂ and R₈₃ are each a radical of the formula XI --CH₂ --R, R₈₄ andR₈₅ together are the radical ═N--R₄₄, and R₈₆ is unsubstituted orsubstituted cyclopentadienyl, R₄₅ --O-- or halogen, or

c) R₈₂, R₈₃ and R₈₄, are each a radical of the formula XI --CH₂ --R, andR₈₅ and R₈₆ together are the radical ═N--R₄₄, or R₈ ₂, R₈₃, R₈₄ and R₈,are a radical of the formula XI --CH₂ --R and R₈₆ is unsubstituted orsubstituted cyclopentadienyl, R₄₅ --O-- or halogen,

where R, R₄₄ and R₄₅ have the above meanings. The above preferredmeanings apply to R, R₄₄ and R₄₅.

Niobium and tantalum compounds which are especially preferably used inthe process according to the invention are those of the formulae IXX,IXXa or IXXb ##STR21## in which Me is Nb(V) or Ta(V),

R_(v) is H, --C(CH₃)₃, --C(CH₃)₂ --C₆ H₅, --C₆ H or --Si(C₁ -C₄ alkyl)₃,

R₆₃ is phenyl or phenyl which is substituted by 1 to 3 C₁ -C₄ alkyl orC₁ -C₄ alkoxy,

R₈₄ in formula IXX is the group --CH₂ --R or F, Cl, Br, linear or, inparticular, branched C₁ -C₄ alkoxy which is unsubstituted or substitutedby fluorine, phenyloxy which is unsubstituted or substituted by C₁ -C₄alkyl or C₁ -C₄ alkoxy, or cyclopentadienyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl;

R₈₂, R₈₃ and R₈₄ in formula IXXa independently of one another are F, Cl,Br, linear or, in particular, branched C₁ -C₄ alkoxy which isunsubstituted or substituted by fluorine, phenyloxy

which is unsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy,or cyclopentadienyl which is unsubstituted or substituted by C₁ -C₄alkyl; and

R₈₂ and R₈₃ in formula IXXb independently of one another are F, Cl, Br,linear or, in particular, branched C₁ -C₄ alkoxy which is unsubstitutedor substituted by fluorine, phenyloxy which is unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or cyclopentadienyl whichis unsubstituted or substituted by C₁ -C₄ alkyl. The alkoxy isparticularly preferably branched alkoxy, which is optionally partly orcompletely substituted by F, for example i-propyloxy, i- and t-butyloxy,hexafluoropopyloxy [sic] or nonafluoropropyloxy.

Some examples of niobium(V) and tantalum(V) compounds are [Cp iscyclopentadienyl and Me is Nb(V) or Ta(V)]: Me[CH₂ Si(CH₃)₃ ]₅, Cp₂Me[(CH₂ C(CH₃)₂ --C₆ H₅)]₃, Me(═N-2,6-dimethylC₆ H₃)(CH₃)₃, Me(═N--C₆H₅)[OC(CH₃)₃ ][CH₂ Si(CH₃)₃)]₂, Me(═N-2,6-diisopropylC₆ H₃)[(CH₂ -C₆H₅)]₃, Me(═N--C₆ H₅)[OCCH₃ (CF₃)₂ ][(CH₂ Si(CH₃)₃)]₂, CpMe[OCCH₃ (CF₃)₂]₂ [(CH₂ -C₆ H₅)]₂, Me(═N-2,6-diisopropylC₆ H₃)[(CH₂ C(CH₃)₂ --C₆ H₅)]₂Cl, Cp₂ Me(CH₃)₂ [OCH(CH₃)₂ ], Me(═N-2,6-dimethylC₆ H₃)[(CH₂ -C₆ H₅ ]₃,CpMe[OCH(CH₃)₂ ]₂ [(CH₂ Si(CH₃)₃)₃)]₂, Cp₂ Me[(CH₂ -C₆ H₅)₃, Me[CH₂Si(CH₃)₃ ]₃ Cl₂, Me[CH₂ Si(CH₃)₃ ]₃ [OCH₂ C(CH₃)₃ ]₂, Cp₂Me[3,5-dimethylC₆ H₃ O)][(CH₂ Si(CH₃)₃)]₂, Me(2,6-diisopropylphenyloxy)₂(CH₃)₃, Cp₂ Me(CH₃)₃, Me(2,6-dimethylphenyloxy)₂ (CH₃)₃, Me[CH₂ Si(CH₃)₃]₃ CpMe[OC(CH₃)₃ ]₂ [(CH₂ -C₆ H₅)]₂ and Cp₂ Me[(CH₂ Si(CH₃)₃)]₃ ].

The niobium and tantalum compounds to be used according to the inventionare known or can be prepared by known and analogous processes startingfrom the optionally substituted metal halides via Grignard reactionsand/or substitution reactions [Schrock, R. R., Murdzeck, J. S., Bazan,G. C., Robbins, J., DiMare, M., O'Regan, M., J. Am. Chem. Soc.,112:3875-3886 (1990)].

5. Other suitable photoactive one-component catalysts are titanium(IV)compounds which contain, bonded to the metal, at least two methyl groupsor two monosubstituted methyl groups, the substituent containing nohydrogen atom in the a position. These compounds are also thermalcatalysts.

The titanium(IV) compounds to be used according to the invention containone metal atom. The methyl group or monosubstituted methyl group whichis bonded to the metal is bonded at least twice, particularly preferablytwo to four times, and especially preferably two or three times, as aligand. This ligand preferably corresponds to the formula XI

    --CH.sub.2 --R                                             (XI)

where R has the meanings and preferred meanings given above.

The other valencies of the titanium atom are preferably satisfied withheat-stable neutral ligands, a large number of which are known. Thenumber of neutral ligands can also exceed the stoichiometricallypossible number (solvates). The definition of heat stability has beengiven in the introduction.

The neutral ligands are, advantageously, identical or different ligands,for example from the group consisting of secondary amines having 2 to 18C atoms, R₄₅ O--, R₄₅ S--, halogen, cyclopentadienyl, bridgedbiscyclopentadienyl, tridentate monoanionic ligands and neutral ligands,for example ethers and amines, in which the R₆₂ independently of oneanother are linear or branched C₁ -C₁₈ alkyl which is unsubstituted orsubstituted by C₁ -C₆ alkoxy or halogen, C₅ - or C₆ cycloalkyl which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen,phenyl which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen, or benzyl orphenylethyl which are unsubstituted or substituted by C₁ -C₆ alkyl, C₁-C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen.

The meanings and preferences of R₄₅, of secondary amines, of halogen asa further ligand on the metal atoms or as a substituent, ofcyclopentadienyl, ethers, nitriles, tertiary amines and phosphines asneutral ligands and of tridentate monoanionic ligands have been givenabove. The meanings and meanings of alkyl, alkoxy or alkoxy as asubstituent in alkoxymethyl or -ethyl have likewise been given above.

In a preferred embodiment, the titanium(IV) compounds correspond, inparticular, to the formulae XX ##STR22## in which at least two,preferably 2 or 3, of the radicals R₈₇ to R₉₀ are a radical --CH₂ --R ofthe formula XI, in which R has the meanings and preferred meanings givenabove; and the other radicals R₈₇ to R₉₀ are secondary amino having 2 to18 C atoms, R₄₅ O--, R₄₅ S--, halogen, cyclopentadienyl or bridgedbiscyclopentadienyl or a neutral ligand, in which the R₄₅ independentlyof one another are linear or branched C₁ -C₁₈ alkyl which isunsubstituted or substituted by C₁ -C₆ alkoxy or halogen, C₅ - or C₆cycloalkyl which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁-C₆ alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen, orbenzyl or phenylethyl which are unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆alkyl)amino, di(C₁ -C₆ alkyl)aminoC₁ -C₃ alkyl or halogen.

In a particularly preferred embodiment, the titanium(IV) compounds ofthe formula XX which are used in the process according to the inventionare those in which

a) R₈₇ to R₉₀ are a radical of the formula XI --CH₂ --R, or

b) R₈₇ and R₈₈ are a radical of the formula XI --CH₂ --R, and R₈₉ andR₉₀ independently of one another are unsubstituted or substitutedcyclopentadienyl, R₄₅ --O-- or halogen, or

c) R₈₇, R₈₈ and R₈₉ are a radical of the formula XI --CH₂ --R, and R₉₀is unsubstituted or substituted cyclopentadienyl, R₄₅ --O-- or halogen,

where R and R₄₅ have the above meanings. The above preferred meaningsapply to R and R₄₅.

Titanium(IV) compounds which are especially preferably used in theprocess according to the invention are those of the formulae XXIa orXXIb ##STR23## in which R_(v) is H, --C(CH₃)₃, --C(CH₃)₂ --C₆ H₅, --C₆H₅ or --Si(C₁ -C₄ alkyl)₃, and

R₈₇ and R₈₈ independently of one another are F, Cl, Br, linear or, inparticular, branched C₁ -C₄ alkoxy which is unsubstituted or substitutedby fluorine, phenyloxy which is unsubstituted or substituted by C₁ -C₄alkyl or C₁ -C₄ alkoxy, or cyclopentadienyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl. The alkoxy is particularly preferablybranched alkoxy, which is unsubstituted or partly or completelysubstituted by F, for example i-propyloxy, i- and t-butyloxy,hexafluoropropyloxy and nonafluoropropyloxy.

In a preferred embodiment of the invention, the titanium(IV) compoundscontain a halogen atom, in particular Cl or Br, bonded to the titaniumif the radical R in the group --CH₂ --R is --SiR₃₈ R₃₉ R₄₀. Compoundswhich are especially preferred are then those of the formula XXII##STR24## in which Y₁ is F, Cl or Br,

R₃₈, R₃₉ and R₄₀ independently of one another are C₁ -C₁₈ alkyl, C₅ - orC₆ -cycloalkyl or phenyl or benzyl which are unsubstituted orsubstituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy; and

R₈₇ is the group --CH₂ --SiR₃₈ R₃₉ R₄₀, F, Cl, Br, linear or, inparticular, branched C₁ -C₄ alkoxy which is unsubstituted or substitutedby fluorine, phenyloxy which is unsubstituted or substituted by C₁ -C₄alkyl or C₁ -C₄ alkoxy, or cyclopentadienyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl. R₃₈, R₃₉ and R₄₀ are preferably C₁ -C₄alkyl, phenyl or benzyl, and

R₈₇ is preferably Cl, C₃ - or C₄ -alkyl which is unsubstituted orsubstituted by fluorine, or phenyl or benzyl which are unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

Some examples of titanium(IV) compounds are [Cp is cyclopentadienyl]:Ti[CH₂ Si(CH₃)₃ ]₄, Ti[OCH(CF₃)₂ ]₂ [(CH₂ Si(CF₃)₃ ]₂, CpTi[(CH₂ C(CH₃)₂-C₆ H₅)]₂ Cl, CpTi[(CH₂ -C₆ H₅)]₃, TiCl₂ [CH₂ Si(CH₃)₃)]₂, [OCH(CF₃)₂]Ti[(CH₂ -C₆ H₅)]₃, CpBrTi[(CH₂ C(CH₃)₂ -C₆ H₅)]₂, CpTi[2,6-dimethylC₆H₃ O)][(CH₂ Si(CH₃)₃)]₂, Ti[OCH(CH₃)₂ ]₂ [(CH₂ -C₆ H₅)]₂, ClTi[OCH(CH₃)₂][(CH₂ Si(CH₃)₃)]₂, CpTi[OCH(CF₃)₂ ][(CH₂ -C₆ H₅)]₂, CpTi(methyl)₃,CpTi(methyl)₂ [OCH(CH₃)₂ ], Ti[CH₂ Si(CH₃)₃ ]₂ Br₂,Ti(2,6-dimethylphenyloxy)₂ (CH₃)₂, Cp₂ Ti(CH₃)₂, Ti[CH₂ Si(CH₃)₃ ]₃[OCH(CH₃)] and Ti(2,6-diisopropylphenyloxy)₂ (CH₃)₂.

The titanium(IV) compounds to be used according to the invention areknown or can be prepared by known and analogous processes starting fromthe metal halides by Grignard reactions or other known substitutionreactions [see Clauss, K., Bestian, H., Justus Liebigs Ann. Chem.,654:8-19 (1962)].

6. Other suitable photocatalytically active compounds are ruthenium orosmium compounds which contain at least one phosphine group, at leastone photolabile ligand, and optionally neutral ligands bonded to themetal atom, a total of 2 to 5 ligands being bonded, and which containacid anions for balancing the charge. Total in the context of theinvention means the sum of the phosphine groups, photolabile ligands andneutral ligands. The neutral ligands are also called non-photolabileligands. Preferably 2 to 4, and particularly preferably 2 or 3, ligandsare bonded in total.

The osmium compounds are also thermally active catalysts. The rutheniumcompounds are also thermal catalysts if the phosphine group contains nolinear alkyl or alkoxy group, but bulky groups, for example secondaryand tertiary alkyl or alkoxy groups (i-propyl or i- and t-butyl), orcycloalkyl groups, or phenyl groups or phenyloxy groups which areunsubstituted or substituted by 1 to 3 C₁ -C₄ alkyl or -alkoxy.

The phosphine group is preferably tertiary phosphines having 3 to 40,more preferably 3 to 30 and particularly preferably 3 to 24 C atoms.

The other valencies of the ruthenium and osmium are preferably satisfiedwith heat-stable neutral ligands, a large number of which are known. Thenumber of neutral ligands can also exceed the stoichiometricallypossible number (solvates).

In the ruthenium and osmium compounds to be used according to theinvention, a monophosphine can be bonded one to three times andpreferably two or three times and a diphosphine can be bonded once tothe metal atom. Preferably 1 or 2 photolabile ligands are bonded in theruthenium and osmium catalysts. The phosphine ligands preferablycorrespond to the formulae XXIII and XXIIIa

    PR.sub.91 R.sub.92 R.sub.93                                (XXIII),

    R.sub.91 R.sub.92 P-Z.sub.1 -PR.sub.91 R.sub.92            (XXIIIa),

in which R₉₁, R₉₂ and R₉₃ independently of one another are H, C₁ -C₂₀alkyl, C₄ -C₁₂ cycloalkyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, or C₆ -C₁₆ aryl which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆alkoxy, or C₇ -C₁₆ aralkyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy; the radicals R₉₁ and R₉₂together are tetra- or pentamethylene which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, ortetra- or pentamethylene which is unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy and fused with 1 or 21,2-phenylene, and R₉₃ has the meaning given above; and

Z₁ is linear or branched C₂ -C₁₂ alkylene which is unsubstituted orsubstituted by C₁ -C₄ alkoxy, 1,2- or 1,3-cycloalkylene which has 4 to 8C atoms and is unsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄alkoxy, or 1,2 or 1,3-heterocycloalkylene which has 5 or 6 ring membersand one heteroatom from the group consisting of O or N and isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy.

The radicals R₉₁, R₉₂ and R₉₃ are preferably identical radicals.

If R₉₁, R₉₂ and R₉₃ are substituted, the substituents are preferably C₁-C₄ alkyl, C₁ -C₄ haloalkyl or C₁ -C₄ alkoxy. Halogen is preferably Cland particularly preferably F. Examples of preferred substituents aremethyl, methoxy, ethyl, ethoxy and trifluoromethyl. R₉₁, R₉₂ and R₉₃ arepreferably substituted by 1 to 3 substituents. Substituents arepreferably in one or both ortho and/or meta positions relative to the Catom of the P--C bond in the phosphine.

Alkyl R₉₁, R₉₂ and R₉₃ can be linear or branched and can preferablycontain 1 to 12, more preferably 1 to 8, and particularly preferably 1to 6 C atoms. Examples of alkyl are methyl, ethyl, n- and i-propyl, n-,i- and t-butyl and the isomers of pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl and eicosyl. Preferred examples are methyl, ethyl,n- and i-propyl, n-, i- and t-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3-or 4-hexyl.

Cycloalkyl R₉₁, R₉₂ and R₉₃ are preferably C₅ -C₈ cycloalkyl, andparticularly preferably C₅ - or C₆ cycloalkyl. Some examples arecyclobutyl, cycloheptyl, cyclooctyl and, in particular, cyclopentyl andcyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-,trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-,bistrifluoromethyl and tristrifluoromethylcyclopentyl and -cyclohexyl.

Aryl R₉₁, R₉₂ and R₉₃ are preferably C₆ -C₁₂ aryl, and particularlypreferably phenyl or naphthyl. Examples of substituted aryl are methyl-,dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-,trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylphenyl.

Aralkyl R₉₁, R₉₂ and R₉₃ are preferably C₇ -C₁₃ aralkyl, where thealkylene group in the aralkyl is preferably methylene. The aralkyl isparticularly preferably benzyl. Examples of substituted aralkyl aremethyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-,trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylbenzyl.

Examples of optionally substituted or fused tetra- or pentamethylenebonded to the P atom are ##STR25##

Other suitable phosphines are cycloaliphatics which have 6 to 8 ringcarbon atoms and are bridged with a ═PRa group, for example ##STR26## inwhich Ra is C₁ -C₆ alkyl, cyclohexyl, benzyl, or phenyl which isunsubstituted or substituted by 1 or 2 C₁ -C₄ alkyl.

Linear or branched alkylene Z₁ is preferably 1,2-alkylene or1,3-alkylene having preferably 2 to 6 C atoms, for example ethylene,1,2-propylene or 1,2-butylene.

Examples of cycloalkylene Z₁ are 1,2- and 1,3-cyclopentylene and 1,2- or1,3-cyclohexylene. Examples of heterocycloalkylene Z₁ are 1,2- and1,3-pyrrolidine, 1,2- and 1,3-piperidine and 1,2- and1,3-tetrahydrofuran.

In a preferred embodiment, the phosphine ligands correspond to theformula XXIII in which R₉₁, R₉₂ and R₉₃ independently of one another areH, C₁ -C₆ alkyl, cyclopentyl or cyclohexyl which are unsubstituted orsubstituted by C₁ -C₄ alkyl, or phenyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkyl [sic] C₁ -C₄ alkoxy ortrifluoromethyl, or benzyl which is unsubstituted or substituted by C₁-C₄ alkyl, C₁ -C₄ alkyl [sic] C₁ -C₄ alkoxy or trifluoromethyl.Particularly preferred examples of phosphine ligands of the formulaXXIII are (C₆ H₅)₃ P, (C₆ H₅ CH₂)₃ P, (C₅ H₁₁)₃ P, (CH₃)₃ P, (C₂ H₅)₃ P,(n-C₃ H₇)₃ P, (i-C₃ H₇)₃ P, (n-C₄ H₉)₃ P, (C₆ H₅)₂ HP, (C₆ H₅ CH₂)₂ HP,(C₅ H₁₁)₂ HP, (C₂ H₅)₂ HP, (n-C₃ H₇)₂ HP, (i-C₃ H₇)₂ HP, (n-C₄ H₉)₂ HP,(C₆ H₅)H₂ P, (n-C₄ H₉)H₂ P, (C₆ H₅ CH₂)H₂ P, (C₅ H₁₁)H₂ P, (CH₃)H₂ P,(CH₃)₂ HP, (C₂ H₅)H₂ P, (n-C₃ H₇)H₂ P, (i-C₃ H₇)H₂ P, PH₃ (2-methyl-C₆H₄)₃ P, (3-CH₃ --C₆ H₄)₃ P, (4-C₂ H₅ --C₆ H₄)₃ P, (4-CH₃ --C₆ H₄)₃ P,(2,4-di-CH₃ --C₆ H₃)₃ P, (2,6-di-CH₃ --C₆ H₃)₃ P, (2-C₂ H₅ --C₆ H₄)₃ P,(3-C₂ H₅ --C₆ H₄)₃ P, (2-n-C₃ H₇ --C₆ H₄)₃ P, (3-n-C₃ H₇ --C₆ H₄)₃ P,(4-n-C₃ H₇ --C₆ H₄)₃ P, (2-i-C₃ H₇ --C₆ H₄)₃ P, (3-i-C₃ H₇ --C₆ H₄)₃ P,(4-i-C₃ H₇ --C₆ H₄)₃ P, (2-n-C₄ H₉ --C₆ H₄)₃ P, (3-n-C₄ H₉ --C₆ H₄)₃ P,(4-n-C₄ H₉ --C₆ H₄)₃ P, (2-i-C₄ H₉ --C₆ H₄)₃ P, 3-i-C₄ H₉ --C₆ H₄)₃ P,(4-i-C₄ H₉ --C₆ H₄)₃ P, (2-t-C₄ H₉ --C₆ H₄)₃ P, (3-t-C₄ H₉ --C₆ H₄)₃ P,(4-t-C₄ H₉ --C₆ H₄)₃ P, (2-CH₃ -6-t-C₄ H₉ --C₆ H₃)₃ P, (3-CH₃ -6-t-C₄ H₉--C₆ H₃)₃ P, (3-CH₃ -6-t-C₄ H₉ --C₆ H₃)₃ P, (2,6-di-t-C₄ H₉ --C₆ H₃)₃ P,(2,3-di-t-C₄ H₉ --C₆ H₃)₃ P and (2,4-di-t-C₄ H₉ --C₆ H₃)₃ P.

Organic or inorganic compounds, atoms or ions which are coordinated ontoa metal centre are designed as ligands for the ruthenium and osmiumcompounds to be used according to the invention.

The meanings and preferred meanings of photolabile ligands andnon-photolabile ligands (also called highly coordinating ligands) havebeen mentioned above.

In a preferred embodiment, the Ru and Os catalysts to be used accordingto the invention contain only photolabile ligands, phosphine groups andanions for balancing the charge. The catalysts which contain an arenegroup as photolabile ligands, a tertiary phosphine group, and mono- orbivalent anions for balancing the charge are especially preferred.

Suitable anions of inorganic or organic acids are, for example, hydride(H.sup.⊖), halide (for example F.sup.⊖, Cl.sup.⊖, Br.sup.⊖ and l.sup.⊖),the anion of an oxygen acid and BF₄.sup.⊖, PF₆.sup.⊖, SbF₆.sup.⊖ orAsF₆.sup.⊖. It should be mentioned that the abovementionedcyclopentadienyl is a ligand and an anion.

Further suitable anions are C₁ -C₁₂ -, preferably C₁ -C₆ -, andparticularly preferably C₁ -C₄ alcoholates, which, in particular, arebranched, for example correspond to the formula R_(x) R_(y) R_(z)C--O.sup.⊖, in which R_(x) is H or C₁ -C₁₀ alkyl, R_(y) is C₁ -C₁₀ alkyland R_(z) is C₁ -C₁₀ alkyl or phenyl, and the sum of the C atoms ofR_(x), R_(y) and R_(z) is 11. Examples are, in particular, i-propyloxyand t-butyloxy.

Other suitable anions are C₃ -C₁₈ -, preferably C₅ -C₁₄ -, andparticularly preferably C₅ -C₁₂ acetylides, which can correspond to theformula R_(w) --C.tbd.C.sup.⊖, in which R_(w) is C₁ -C₁₆ alkyl,preferably α-branched C₃ -C₁₂ alkyl, for example of the formula R_(x)R_(y) R_(z) C--, or is phenyl or benzyl which are unsubstituted orsubstituted by 1 to 3 C₁ -C₄ alkyl or C₁ -C₄ alkoxy. Some examples arei-propyl-, i- and t-butyl-, phenyl-, benzyl-, 2-methyl-, 2,6-dimethyl-,2-i-propyl-, 2-i-propyl-6-methyl-, 2-t-butyl-, 2,6-di-t-butyl- and2-methyl-6-t-butylphenylacetylide.

The meanings and preferred meanings of anions of oxygen acids have beenmentioned above.

H.sup.⊖, F.sup.⊖, Cl.sup.⊖, Br.sup.⊖, BF₄.sup.⊖, PF₆.sup.⊖, SbF₆.sup.⊖,AsF₆.sup.⊖, CF₃ SO₃.sup.⊖, C₆ H₅ --SO₃.sup.⊖, 4-methyl-C₆ H₅ -SO₃.sup.⊖,2,6-dimethyl-C₆ H₅ --SO₃.sup.⊖, 2,4,6-trimethyl-C₆ H₅ --SO₃.sup.⊖ and4-CF₃ --C₆ H₅ --SO₃.sup.⊖ and cyclopentadienyl (Cp.sup.⊖) areparticularly preferred.

The number of non-photolabile ligands depends on the number of phosphinegroups, the size of the non-photolabile ligands and the number ofphotolabile ligands.

In a preferred embodiment, the ruthenium and osmium compoundsparticularly preferably correspond to one of the formulae XXIV to XXIVf

    R.sub.97 L.sub.1 Me.sup.2+ (Z.sup.n-).sub.2/n              (XXXIV),

    R.sub.97 L.sub.2 L.sub.3 Me.sup.2+ (Z.sup.n-).sub.2/n      (XXIVa),

    (R.sub.97).sub.2 L.sub.2 Me.sup.2+ (Z.sup.n-).sub.2/n      (XXIVb),

    (R.sub.97).sub.3 L.sub.2 Me.sup.2+ (Z.sup.n-).sub.2/n      (XXIVc)

    R.sub.97 L.sub.1 L.sub.2 Me.sup.2+ (Z.sup.n-).sub.2/n      (XXIVd),

    R.sub.97 L.sub.2 L.sub.2 Me.sup.2+ (Zn-).sub.2/n           (XXIVe),

    R.sub.97 L.sub.1 L.sub.3 Me.sup.2+ (Z.sup.n-)              (XXIVf),

in which

R₉₇ is a tertiary phosphine of the formula XXIII or XXIIIa;

Me is Ru or Os;

n is the numbers 1, 2 or 3;

Z is the anion of an inorganic or organic acid;

(a) L₁ is an arene or heteroarene ligand;

(b) L₂ is a monovalent photolabile ligand different from L₁ ; and

(c) L₃ is a monovalent non-photolabile ligand.

For R₉₇, L₈, L₉ and L₁₀ [sic], the preferred meanings stated above forthe individual meanings apply.

In the formulae XXIV to XXIVf, n is preferably 1 or 2 and especially 1.For R₉₇, the preferred meanings stated for the phosphine ligands of theformula XXIII apply, and in particular the phosphines are tertiaryphosphines.

Ruthenium and osmium compounds which are especially preferably used inthe process according to the invention are those of one of the formulaeXXV to XXVf

    (R.sub.94 R.sub.95 R.sub.96 P)L.sub.8 Me.sup.2+ (Z.sup.1-).sub.2 (XXV),

    (R.sub.94 R.sub.95 R.sub.96 P).sub.2 L.sub.9 Me.sup.2+ (Z.sup.1-).sub.2(XXVa),

    (R.sub.94 R.sub.95 R.sub.96 P)L.sub.9 L.sub.10 Me.sup.2+ (Z.sup.1-).sub.2(XXVb),

    (R.sub.94 R.sub.95 R.sub.96 P).sub.3 L.sub.9 Me.sup.2+ (Z.sup.1-).sub.2(XXVc),

    (R.sub.94 R.sub.95 R.sub.96 P)L.sub.9 L.sub.9 Me.sup.2+ (Z.sup.1-).sub.2(XXVd),

    (R.sub.94 R.sub.95 R.sub.96 P)L.sub.8 L.sub.10 Me.sup.2+ (Z.sup.1-).sub.2(XXVe)

    (R.sub.94 R.sub.95 R.sub.96 P)L.sub.8 (L.sub.9).sub.m Me.sup.2+ (Z.sup.1-).sub.2                                          (XXVf)

n which

Me is Ru or Os;

Z in formulae XXV to XXVe is H.sup.⊖, cyclopentadienyl, Cl.sup.⊖,Br.sup.⊖, BF₄.sup.⊖, PF₆.sup.⊖, SbF₆.sup.⊖, AsF₆.sup.⊖,

CF₃ SO₃.sup.⊖, C₆ H₅ --SO₃.sup.⊖, 4-methyl-C₆ H₅ --SO₃.sup.⊖,3,5-dimethyl-C₆ H₅ --SO ₃.sup.⊖, 2,4,6-trimethyl-C₆ H₅ --SO₃.sup.⊖ and4-CF₃ --C₆ H₅ --SO₃.sup.⊖ and in formula XXVf is H.sup.⊖,cyclopentadienyl, BF₄.sup.⊖, PF₆.sup.⊖, SbF₆.sup.⊖,

AsF₆.sup.⊖, CF₃ SO₃.sup.⊖, C₆ H₅ --SO₃.sup.⊖, 4-methyl-C₆ H₅--SO₃.sup.⊖, 2,6-dimethyl-C₆ H₅ --SO₃.sup.⊖, 2,4,6-trimethyl-C₆ H₅--SO₃.sup.⊖ or 4-CF₃ --C₆ H₅ --SO₃.sup.⊖,

R₉₄, R₉₅ and R₉₆ independently of one another are C₁ -C₆ alkyl or-alkoxy, cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxywhich are unsubstituted or substituted by 1 to 3 C₁ -C₄ alkyl, or phenylor benzyl or phenyloxy or benzyloxy which are unsubstituted orsubstituted by 1 to 3 C₁ -C₄ alkyl;

L₈ is C₆ -C₁₆ arene or C₅ -C₁₆ heteroarene which are unsubstituted orsubstituted by 1 to 3 C₁ -C₄ alkyl, C₁ -C₄ alkoxy, --OH, --F or Cl;

L₉ is C₁ -C₆ alkyl-CN, benzonitrile or benzylnitrile; and

L₁₀ is H₂ O or C₁ -C₆ alkanol.

Preferred arenes and heteroarenes are benzene, toluene, xylene,trimethylbenzene, naphthalene, biphenyl, anthracene, acenaphthene,fluorene, phenanthrene, pyrene, chrysene, fluoranthrene, furan,thiophene, pyrrole, pyridine, γ-pyran, γ-thiopyran, pyrimidine,pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran,dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole,isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene,phenazine, phenoxazine, phenothiazine, triazines, thianthrene andpurine. More preferred arenes and heteroarenes are benzene, naphthalene,cumene, thiophene and benzothiophene. The arene is especially preferablybenzene or a benzene which is substituted by C₁ -C₄ alkyl, such as, forexample, toluene, xylene, isopropylbenzene, tert-butylbenzene or cumene,and the heteroarene is preferably thiophene.

If the preparation of the ruthenium and osmium catalysts is carried outin solvents which can coordinate to a metal atom, such as, for example,alkanols, solvated Ru/Os cation complexes which are also included in thescope of the use according to the invention can form.

Some examples of ruthenium and osmium compounds to be used according tothe invention are [Tos is tosylate]: (C₆ H₁₁)₂ HPRu(p-cumene)Cl₂, (C₆H₁₁)₃ PRu(p-cumene)Cl₂, (C₆ H₁₁)₃ PRu(p-cumene)(Tos)₂, (C₆ H₁₁)₃PRu(p-cumene)Br₂, (C₆ H₁₁)₃ PRu(p-cumene)ClF, (C₆ H₁₁)₃ PRu(C₆H₆)(Tos)₂, (C₆ H₁₁)₃ PRu(CH₃ --C₆ H₅)(Tos)₂, (C₆ H₁₁)₃ PRu(i-C₃ H₇ --C₆H₅)(Tos)₂, (C₆ H₁₁)₃ PRu(chrysene)(Tos)₂, (C₆ H₁₁)₃ PRu(biphenyl)(Tos)₂,(C₆ H₁₁)₃ PRu(anthracene)(Tos)₂, (C₆ H₁₁)₃ PRu(C₁₀ H₈)(Tos)₂, (i-C₃ H₇)₃PRu(p-cumene)Cl₂, (CH₃)₃ PRu(p-cumene)Cl₂, (n-C₄ H₉)₃ PRu(p-cumene)Cl₂,[(C₆ H₁₁)₃ P]₂ RuCH₃ -CN)(Tos)₂, (C₆ H₁₁)₃ PRu(CH₃ -CN)(C₂ H₅-OH)(Tos)₂, (C₆ H₁₁)₃ PRu(p-cumene)(CH₃ -CN)₂ (PF₆)₂, (C₆ H₁₁)₃PRu(p-cumene)(CH₃ -CN)₂ (Tos)₂, (n-C₄ H₉)₃ PRu(p-cumene)(CH₃ -CN)₂(Tos)₂, (C₆ H₁₁)₃ PRu(CH₃ -CN)₂ Cl₂, (C₆ H₁₁)₃ PRu(CH₃ -CN)₂ Cl₂, (C₆H₁₁)₃ PRu(p-cumene)(C₂ H₅ OH(BF₄)₂, (C₆ H₁₁)₃ PRu(p-cumene)(C₂ H₅OH(BF₄)₂, (C₆ H₁₁)₃ PRu(p-cumene)(C₂ H₅ OH₂ (PF₆)₂, (C₆ H₁₁)₃ Pru(C₆H₁₁)(C₂ H₅ OH(Tos)₂, (C₆ H₁₁)₃ POs(p-cumene)Cl₂, (i-C₃ H₇)₃POs(p-cumene)Cl₂, (CH₃)₃ POs(p-cumene)Cl₂, (C₆ H₅)₃ POs(p-cumene)Cl₂ andRuCl₂ (p-cumene)[(C₆ H₁₁)₂ PCH₂ CH₂ P(C₆ H₁₁)₂ ].

The ruthenium and osmium compounds to be used according to the inventionare known or can be prepared by known and analogous processes startingfrom the metal halides (for example MeX₃ or [Me-areneX₂ ]₂ and reactionwith phosphines and ligand-forming agents.

7. Other suitable one-component catalysts are divalent-cationicruthenium or osmium compounds with a metal atom to which are bonded,acts [sic], 1 to 3 tertiary phosphine ligands with, in the case of theruthenium compounds, sterically exacting substituents, optionallynon-photolabile neutral ligands and anions for charge balancing, withthe proviso that in ruthenium (trisphenylphosphine) dihalides orhydride-halides, the phenyl groups are substituted by C₁ -C₁₈ alkyl, C₁-C₁₈ haloalkyl or C₁ -C₁₈ alkoxy.

The ruthenium and osmium compounds preferably contain 2 or 3 tertiaryphosphine groups. Phosphine groups in the context of the invention areunderstood as meaning tertiary phosphines. The number of additionalnon-photolabile neutral ligands depends on the one hand on the number ofphosphine ligands and on the other hand on the valency of the neutralligands. Monovalent neutral ligands are preferred.

In a preferred embodiment, the divalent-cationic ruthenium and osmiumcompounds to be used according to the invention contain 3 phosphinegroups and 2 monovalent anions for charge balancing; or 3 phosphinegroups, two monovalent or one divalent non-photolabile neutral ligandand two monovalent anions for charge balancing; or 2 phosphine groups,one monoanionic, additionally monovalent non-photolabile neutral ligandsand one monovalent anion for charge balancing.

The meanings and preferred meanings of non-photolabile ligands (alsocalled highly coordinating ligands) have been mentioned above.

Sterically exacting substituents in the context of the invention areunderstood as meaning those which shield the ruthenium and osmium atomssterically. It has thus been found, surprisingly, that linear alkylgroups as substituents in the phosphine ligands give ruthenium compoundswithout any thermal activity for metathesis polymerization of strainedcycloolefins. It has also been found that in the case of osmiumcompounds, linear alkyl groups as substituents in the phosphine ligandssurprisingly have an excellent thermocatalytic activity for themetathesis polymerization of strained cycloolefins; however, phosphineligands with sterically exacting substituents are also preferably usedfor the osmium compounds. It has furthermore been found that the stericshielding of triphenylphosphine ligands is inadequate in rutheniumdihalides and ruthenium hydride-halides, and such catalysts have only amoderate catalytic activity for the metathesis polymerization ofstrained cycloolefins. Surprisingly, the catalytic activity can beincreased considerably if the tertiary phosphine groups contain phenylwhich is substituted by alkyl or alkoxy groups.

The meanings and preferred meanings of phosphine ligands have beenmentioned above. With particular preference, alkyl R₉₁, R₉₂ and R₉₃ areα-branched alkyl, for example of the formula --CR_(b) R_(c) R_(d), inwhich R_(b) is H or C₁ -C₁₂ alkyl, R_(c) is C₁ -C₁₂ alkyl and R_(d) isC₁ -C₁₂ alkyl or unsubstituted or C₁ -C₄ alkyl- or C₁ -C₄alkoxy-substituted phenyl, and the sum of the C atoms in the radical--CR_(b) R_(c) R_(d) is from 3 to 18.

In the osmium compounds used, R₉₁, R₉₂ and R₉₃ can also be linear alkylhaving 1 to 18, preferably 1 to 12, more preferably 1 to 8, andparticularly preferably 1 to 6 C atoms, for example, methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.

In a preferred embodiment, the phosphine ligands correspond to theformula XXIII, in which R₉₁, R₉₂ and R₉₃ independently of one anotherare α-branched C₃ -C₈ alkyl, cyclopentyl or cyclohexyl which areunsubstituted or substituted by C₁ -C₄ alkyl, or phenyl which isunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkyl [sic] C₁ -C₄alkoxy or trifluoromethyl. Particularly preferred examples of phosphineligands of the formula XXIII are (C₆ H₅)₃ P, (C₅ H₉)₃ P, (i-C₃ H₇)₃ P,(C₆ H₁₁)3P, (i-C₄ H₉)₃ P, (t-C₄ H₉)₃ P, [C₂ H₅ CH(CH₃)]₃ P, [C₂ H₅-CH(CH₃)₂ ]₃ P, (2-methylphenyl)₃ P, (2,3-dimethylphenyl)₃ P,(2,4-dimethylphenyl)₃ P, (2,6-dimethylphenyl)₃ P,(2-methyl-4-i-propylphenyl)₃ P, (2-methyl-3-i-propylphenyl)₃ P,(2-methyl-5-i-propylphenyl)₃ P, (2,4-di-t-butylphenyl)₃ P,(2-methyl-6-i-propylphenyl)₃ P, (2-methyl-3-t-butylphenyl)₃ P,(2,5-di-t-butylphenyl)₃ P, (2-methyl4-t-butylphenyl)₃ P,(2-methyl-5-i-butylphenyl)₃ P, (2,3-di-t-butylphenyl)₃ P and(2,6-di-t-butylphenyl)₃ P.

Examples of and preferred meanings for suitable anions have beenmentioned above.

In a preferred embodiment, the ruthenium and osmium compoundsparticularly preferably correspond to the formulae XXVI, XXVIa, XXVIb,XXVIc and XXVId

    Me.sup.2⊕ (L.sub.11).sub.2 (L.sub.12)(Y.sub.1.sup.⊖).sub.2(XXVI)

    Me.sup.2⊕ (L.sub.11).sub.3 (Y.sub.1.sup.⊖).sub.2 (XXVIa)

    Me.sup.2⊕ (L.sub.11).sub.2 L.sub.13 ((Y.sub.1.sup.⊖)(XXVIb)

    Me.sup.2⊕ (L.sub.11).sub.3 L.sub.14 (Y.sub.1.sup.⊖).sub.2(XXVIc)

    Me.sup.2⊕ L.sub.1 (L.sub.2).sub.3 (Y.sub.1.sup.⊖).sub.2 (XXVId)

in which

Me is Ru or Os;

Y₁ is the anion of a monobasic acid;

L₁₁ is a phosphine of the formula XXIII or XXIIIa,

L₁₂ is a neutral ligand;

L₁₃ is a cyclopentadienyl which is unsubstituted or substituted by C₁-C₄ alkyl; and

L₁₄ is CO.

The above preferred meanings apply to the individual meanings of L₁₁,L₁₂, L₁₃ and Y₁.

In a particularly preferred embodiment, L₁₂ in formula XXVI is a C₁ -C₄alkanol, Y₁ in formula XXVIb is Cl or Br, Y₁ in formula XXVIc is H, andL₁₁ in the formulae XXVI to XXVIc is tri-i-propylphosphine,tricyclohexylphosphine, triphenylphosphine or triphenylphosphine whichis substituted by 1 to 3 C₁ -C₄ alkyl in the phenyl groups.

The ruthenium and osmium compounds to be used according to the inventionare known or can be prepared by known and analogous processes startingfrom the metal halides (for example MeX₃, [Me(diolefin)X₂ ]₂ or[Me-areneX₂ ]₂ and reaction with phosphines and agents which formligands.

The composition according to the invention can additionally compriseother open-chain, strained cyclic and/or strained polycyclic fusedolefins which form metathesis polymers, these olefins preferably alsocontaining further double bonds and contributing to the formation ofcrosslinked polymers. The cyclic olefins can be monocyclic or polycyclicfused ring systems, for example with 2 to 4 rings, which areunsubstituted or substituted and can contain heteroatoms, such as, forexample, O, S, N or Si, in one or more rings and/or fused aromatic orheteroaromatic rings, such as, for example, o-phenylene, o-naphthylene,o-pyridinylene or o-pyrimidinylene. The individual cyclic rings cancontain 3 to 16, preferably 3 to 12, and particularly preferably 3 to 8ring members. The cyclic olefins can contain further nonaromatic doublebonds, preferably 2 to 4 such additional double bonds, depending on thering size. The ring substituents are those which are inert, that is tosay do not impair the chemical stability of the one-component catalysts.A large number of such olefins and cycloolefins are known, and they areobtainable in a simple manner by Diels-Alder reactions of cyclodienesand cycloolefins or polycyclic or polycyclic fused olefins. Thesecycloolefins can correspond, for example, to the formula IIa ##STR27##in which Q₁ and Q₂ have the meanings given for radicals of the formulaII, including the preferred meanings.

Some preferred examples of compounds of the formula IIa are norborneneand norbornene derivatives. Specific examples are: ##STR28##

The composition according to the invention may additionally comprisefurther non-volatile open-chain comonomers which form copolymers withthe strained cycloolefins. With the use of, for example, dienes at thesame time, it is possible for crosslinked polymers to form. Someexamples of such comonomers are olefinically mono- or diunsaturatedcompounds such as olefins and dienes from the group pentene, hexene,heptene, octene, decene, dodecylene, acrylic and methacrylic acid, theiresters and amides, vinyl ethers, styrene, butadiene, isoprene andchlorobutadiene.

The other olefins capable of metathesis polymerization are present inthe composition according to the invention in an amount, for example, ofup to 80% by weight, preferably from 0.1 to 80% by weight, morepreferably from 0.5 to 60% by weight and, with particular preference,from 5 to 40% by weight, based on the total amount of compounds of theformula I and other olefins capable of metathesis polymerization.

Catalytic amounts in the context of the present invention preferablymeans an amount of 0.001 to 20 mol %, more preferably 0.01 to 15 mol %,particularly preferably 0.01 to 10 mol %, and especially preferably 0.01to 5 mol %, based on the amount of the monomer. Because of the highphotocatalytic activity of ruthenium and osmium catalysts containingphosphine groups, amounts of 0.001 to 2 % by weight are especiallypreferred in this case.

The composition according to the invention can comprise solvents,especially if they are [sic] used for the production of coatings.

Suitable inert solvents are, for example, protic polar and aproticsolvents, which can be used by themselves or in mixtures of at least twosolvents. Examples are: ethers (dibutyl ether, tetrahydrofuran, dioxane,ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethylor diethyl ether, diethylene glycol diethyl ether, triethylene glycoldimethyl ether), halogenated hydrocarbons (methylene chloride,chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane,1,1,2,2-tetrachloroethane), carboxylic acid esters and lactones (ethylacetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate,γ-butyrolactone, δ-valerolactone, pivalolactone), carboxylic acid amidesand lactams (N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, tetramethylurea, hexamethylphosphoric acidtriamide, γ-butyrolactam, ε-caprolactam, N-methylpyrrolidone,N-acetylpyrrolidone, N-methylcaprolactam), sulfoxides (dimethylsulfoxide), sulfones (dimethyl sulfone, diethyl sulfone, trimethylenesulfone, tetramethylene sulfone), tertiary amines (N-methylpiperidine,N-methylmorpholine), aliphatic and aromatic hydrocarbons, such as, forexample, petroleum ether, pentane, hexane, cyclohexane,methylcyclohexane, benzene or substituted benzenes (chlorobenzene,o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene,xylene) and nitriles (acetonitrile, propionitrile, benzonitrile,phenylacetonitrile). Preferred solvents are aprotic polar and non-polarsolvents.

The choice of solvents depends chiefly on the properties of theone-component catalysts, which should not be deactivated by the solventsused. Ruthenium and osmium catalysts can be used together with polarprotic solvents, such as, for example, water or alkanols. Thesecatalysts are also insensitive to air, oxygen and moisture, andcorresponding crosslinkable compositions can be processed withoutparticular protective measures. In the case of the other one-componentcatalysts, the exclusion of oxygen and moisture is advisable. Thecompositions are storage-stable, storage in the dark being advisablebecause of the sensitivity to light. The composition according to theinvention can comprise formulation auxiliaries. Known auxiliaries areantistatics, antioxidants, light stabilizers, plasticizers, dyes,pigments, fillers, reinforcing fillers, lubricants, adhesion promoters,viscosity-increasing agents and mould release auxiliaries. The fillerscan be present in surprisingly high proportions without adverselyaffecting the polymerization, for example in amounts of up to 70% byweight, preferably from 1 to 70% by weight, more preferably from 5 to60% by weight, with particular preference from 10 to 50% by weight and,especially preferably, from 10 to 40% by weight, based on thecomposition. Fillers and reinforcing fillers for improving the optical,physical, mechanical and electrical properties have been disclosed inlarge numbers. Some examples are glass and quartz in the form ofpowders, spheres and fibres, metal oxides and semi-metal oxides,carbonates such as MgCO₃, CaCO₃, dolomite, metal sulfates such as gypsumand heavy spar, natural and synthetic silicates such as talc, zeolites,wollastonite, felspars, aluminas such as china clay, ground minerals,whiskers, carbon fibres, polymer fibres or polymer powders, and carbonblack. Viscosity-increasing agents are, in particular, metathesispolymers which have olefinically unsaturated groups and can beincorporated into the polymer in the course of polymerization. Suchmetathesis polymers are known and are obtainable commercially, forexample, under the trade name Vestenamere®. Other viscosity-increasingagents are polybutadiene, polyisoprene or polychlorobutadiene, and alsocopolymers of butadiene, isoprene and chloroprene with olefins. Theviscosity-increasing agents can be present in an amount of from 0.1 to50% by weight, preferably from 1 to 30% by weight, and with particularpreference, from 1 to 20% by weight based on the composition. Whenfillers are used it is judicious to obtain optical transparency for thepolymerization or to carry out the polymerization in thin layers.

The invention also relates to a process for the preparation ofcrosslinked polymers by metathesis polymerization, which ischaracterized in that a composition of

(a) at least one compound of the formula I

    (A).sub.n --B                                              (I),

in which A is the radical of a strained cycloolefin, B is a direct bondor an n-valent bridging group and n is an integer from 2 to 8, and

(b) a catalytic amount of at least one one-component catalyst for ametathesis polymerization which can be activated by heat or radiation,with the exception of norbornenecarboxylic acid (norbornenemethyl) esterof the formula ##STR29## in combination with a catalytic amount of atleast one heat-stable molybdenum(VI) or tungsten(VI) compound whichcontains at least two methyl groups or two monosubstituted methyl groupsbonded to the metal, the substituent containing no hydrogen atom in theα position,

(c) is subjected to polymerization by heating,

(d) is subjected to polymerization by irradiation,

(e) is subjected to polymerization by heating and irradiation,

(f) the one-component catalyst is activated by brief heating and thepolymerization is ended by irradiation, or

(g) the one-component catalyst is activated by brief irradiation and thepolymerization is ended by heating.

Heating can mean a temperature of 50 to 300° C., preferably 60 to 250°C., particularly preferably 60 to 200° C., and especially preferably 60to 150° C. The polymerization times especially depend on the catalystactivity, and the time can extend from minutes to several hours.

In the process according to the invention, it is not necessary tomaintain the irradiation of the reaction mixture over the entireduration of the reaction. Once the polymerization has been initiatedphotochemically, the subsequent course of the reaction takes placeindependently, even in the dark. The irradiation is advantageouslycarried out with light having a wavelength in the range from 50 nm to1000 nm, preferably in the range from 200 nm to 500 nm and especiallypreferably in the UV range. The duration of the irradiation depends onthe nature of the light source. Suitable sources of irradiation are, forexample, the sun; laser, X-ray and, in particular, UV radiation sources.UV lasers or UV lamps are preferably employed according to theinvention. The catalyst can be irradiated both before or during as wellas after addition of the monomer.

Suitable irradiation times are from one second to several hours, inparticular minutes to hours. The sequence of addition of monomers andcatalyst is not critical. The monomer can be both initially introducedinto the reaction vessel and added after introduction of catalyst.Likewise, the catalyst can be pre-irradiated and the monomer can then beadded. It is furthermore also possible to irradiate the solutioncomprising catalyst and monomer.

In the case of irradiation, the process according to the invention ispreferably carried out at room temperature to slightly elevatedtemperature. An increase in temperature serves to increase the rate ofreaction. The catalysts used initiate thermal metathesis polymerizationper se, with crosslinking, at the temperatures chosen only inexceptional cases. At the temperatures chosen to accelerate thereaction, photopolymerization therefore chiefly takes place. However, itshould be mentioned that the catalysts can be converted intothermoactive catalysts by adequate irradiation.

In particular, the process according to the invention is carried outwith irradiation preferably at temperatures of -20 to +110° C.,particularly preferably 20 to 80° C.

The duration of irradiation especially depends on the desired reactionprocedure. Brief irradiation is chosen, for example, if thepolymerization is to be only initiated by irradiation and is to be endedby heating. Brief can mean an irradiation time of up to 60 seconds,preferably 5 to 60 seconds, and particularly preferably 10 to 40seconds. A longer irradiation time is chosen, for example, if thepolymerization is to be carried out chiefly with irradiation and thefinal polymerization is to be ended only by after-heating.

A quite particular and surprising advantage of the process according tothe invention is that the one-component catalysts used act as thermalcatalysts after the irradiation. This results in the possibility ofcontinuing and ending the polymerization by supplying heat after a shortirradiation time, which offers economic and industrial advantages invarious areas of the production of shaped articles or coatings.

The present invention furthermore relates to crosslinked metathesispolymers of at least one compound of the formula I

    (A).sub.n --B                                              (I)

in which A is the radical of a strained cycloolefin, B is a direct bondor an n-valent bridging group and n is an integer from 2 to 8, and ifappropriate other monomers capable of metathesis polymerization, withthe exception of norbornenecarboxylic acid norbornenemethyl ester.

Materials for production of shaped articles by machining, or, directly,all types of shaped articles, as well as coatings and images in relief,can be produced by the process according to the invention.

The polymers according to the invention can have very differentproperties, depending on the monomer used. Some are distinguished by avery high permeability to oxygen, low dielectric constants, good heatstability and low absorption of water. Others have outstanding opticalproperties, such as, for example, high transparency and low refractiveindices. The low shrinkage is furthermore to be emphasized inparticular. They can therefore be used in very different industrialfields.

As layers on the surfaces of carrier materials, the compositionsaccording to the invention are distinguished by a high adhesivestrength. The coated materials are furthermore distinguished by a veryhigh surface smoothness and gloss. Of the good mechanical properties,the low shrinkage and the high impact strength are to be emphasized inparticular, as well as the heat stability. Easy removal from the mouldduring processing in moulds and the high resistance to solvents arefurthermore to be mentioned.

These polymers are suitable for the production of medical equipment,implants or contact lenses; for the production of electronic components;as binders for coatings; as photocurable compositions for modelconstruction or as adhesives for gluing substrates with low surfaceenergies (for example Teflon, polyethylene and polypropylene), as wellas a photopolymerizable composition in stereolithography. Thecompositions according to the invention can also be used for theproduction of coatings by photopolymerization, it being possible on theone hand for clear (transparent) and even pigmented compositions to beused. Both white and colored pigments can be used.

The compositions according to the invention are particularly suitablefor the production of protective coatings and images in relief. Theinvention also relates to a variant of the process according to theinvention for the production of coated materials or relief images oncarrier materials in which a composition according to the invention andoptionally solvent is applied as a layer to a carrier, for example bydipping, brushing, pouring, rolling, knife-coating or whirler pouringprocesses, the solvent is removed, if appropriate, and the layer isirradiated or heated for polymerization, or the layer is irradiatedthrough a photomask and the non-irradiated portions are then removedwith a solvent. This can be followed by thermal conditioning. Surfacesof substrates can be modified or protected by this process, or, forexample, printed circuits, printing plates or printing rolls can beproduced. In the production of printed circuits, the compositionsaccording to the invention can also be employed as solder resists. Otherpossible uses are the production of screen printing masks and the use asradiation-curable printing inks for offset, screen and flexographicprinting.

The present invention furthermore relates to a coated carrier material,which is characterized in that a layer of a composition according to theinvention is applied to a substrate.

The present invention also relates to a coated substrate with a curedlayer of a composition according to the invention. The exceptionallyhigh adhesive strength of the layers, even on metal surfaces, deservesparticular emphasis, even if the polymers are pure hydrocarbon polymers.

Suitable carrier materials are, for example, those of glass, minerals,ceramics, plastics, wood, semi-metals, metals, metal oxides and metalnitrides. The layer thicknesses essentially depend on the desired useand can be, for example, 0.1 to 1000 μm, preferably 0.5 to 500 μm,particularly preferably 1 to 100 μm. The coated materials aredistinguished by a high adhesive strength and good thermal andmechanical properties.

The production of the coated materials according to the invention can becarried out by known methods, such as, for example, brushing,knife-coating, pouring processes, such as curtain coating or whirlerpouring.

The compositions according to the invention are also suitable for thepreparation of rubber-like or thermoplastic polymers, which can becrosslinked still further if they contain reactive groups, such as, forexample, (meth)acrylate or epoxide groups.

The compositions according to the invention can also be used asadhesives, which can be cured by heat or by means of radiation, forfirmly joining the most diverse materials, it being possible foroutstanding peel strength to be achieved.

The polymers according to the invention are in particular alsodistinguished by very good physico-mechanical properties, such as, forexample, high heat stability, breaking and flexural strength and impactstrength and outstanding electrical properties, such as, for example,low surface tensions and charges (very low ε and tan δ values), inaddition to the high adhesive strength, the outstanding processingproperties, the good surface properties (smoothness, gloss), the highcrosslinking density and the resistance to solvents and other liquids.The high permeability to oxygen and the low absorption of water arefurthermore to be mentioned. Polymers built up only from carbon andhydrogen are particularly valuable ecologically, since they can berecycled completely, for example by pyrrolysis [sic].

The following examples illustrate the invention in more detail.

A) Preparation of Biscycloolefins

EXAMPLE A1

Preparation of Compound No. 0 (see EP 287,762).

70 g (0.86 mol) of 1,5-hexadiene and 56 g (0.42 mol) ofdicyclopentadiene are mixed in an autoclave and the mixture is heated at190° C. for 8 hours. After cooling, the mixture is distilled in vacuo.32.6 g (36%) of product are obtained as a colourless liquid at 80 to110° C. under 0.28 to 0.30 mbar; n_(D) ²⁰ =1.525.

Elemental analysis: calculated C 89.65; H 10.35; found C 89.72; H 10.13.

EXAMPLE A2

Preparation of Compound No.2.

35 g (0.32 mol) 1,7-octadiene and 28 g (0.21 mol) of dicyclopentadieneare mixed in an autoclave and the mixture is heated at 190° C. for 8hours. After cooling, the mixture is distilled in vacuo. 6.7 g (13%) ofproduct are obtained as a colourless liquid at 100° C. under 0.21 mbar;n_(D) ²⁰ =1.516.

Elemental analysis: calculated C 89.19; H 10.81; found C 89.50; H 10.60.

EXAMPLE A3

Preparation of Compound No.3

34.6 g (0.25 mol) of 1,5-decadiene and 33.1 g (0.25 mol) ofdicyclopentadiene are mixed in an autoclave and the mixture is heated at190° C. for 8 hours. After cooling, the mixture is distilled in vacuo.11.4 g (17%) of product are obtained as a colourless liquid at 80 to100° C. under 0.24 mbar; n_(D) ²⁰ =1.504, the liquid becoming solid atroom temperature.

Elemental analysis: calculated C 88.82; H 11.18; found C 88.62; H 11.18.

EXAMPLE A4

Preparation of Compound No. 20

99.7 g (0.40 mol) of triallyl cyanurate and 79.3 g (0.6 mol) ofdicyclopentadiene are mixed in an autoclave and the mixture is heated at190° C. for 8 hours. After cooling, 160 g (89.4%) of a brownish resinoussolid having a melting point of of [sic] 50° C., which is soluble intoluene and chloroform, are obtained.

Elemental analysis: calculated C 72.46; H 7.43; N 9.39. found C 72.21; H7.52; N 9.32.

A') Preparation of Comonomers

EXAMPLE A'1

Preparation of Compound No.59

100 g (0.92 mol) of 1,5-cyclooctadiene and 200 g (1.51 mol) ofdicyclopentadiene are mixed together with 0.4 g of hydrquinone [sic]monomethyl ether in an autoclave and the mixture is heated at 190° C.for 3 hours. After cooling, it is distilled in vacuo. 73.5 9 (33%) ofproduct are obtained as a colourless liquid at 110° C. under 4.6 mbar;n_(D) ²⁰ =1.534. MS: M⁺ =240.

Elemental analysis: calculated C 89.92; H 10.08; found C 90.11; H 9.04.

EXAMPLE A'2

Preparation of Compound No.65

64.9 g (0.40 mol) of 1,5,9-cyclododecatriene and 79.3 g (0.60 mol) ofdicyclopentadiene are mixed in an autoclave and the mixture is heated at190° C. for 8 hours. After cooling, it is distilled in vacuo. 22.6 g(16%) of product are obtained as a colourless liquid at 50 to 60° C.under 0.04 mbar; n_(D) ²⁰ =1.541. MS: M⁺ =360.

Elemental analysis: calculated C 89.94; H 10.06; found C 89.96; H 9.90.

EXAMPLE A'3

Preparation of Compound No.63

92.1 g (1.00 mol) of cycloheptatriene and 198.3 g (1.50 mol) ofdicyclopentadiene are mixed in an autoclave and the mixture is heated at190° C. for 8 hours. After cooling, it is distilled in vacuo. 80.6 g(28%) of product are obtained as a colourless liquid at 75° C. under0.12 mbar; n_(D) ²⁰ =1.542. MS: M⁺ =290.

Elemental analysis: calculated C 90.98; H 9.02; found C 90.71; H 9.31.

EXAMPLE A'4

Preparation of Compound No. 64

100 g (1.09 mol) of norbornadiene and 50 g (0.38 mol) ofdicyclopentadiene are mixed together with 0.2 g of hydroquinonemonomethyl ether in an autoclave and the mixture is heated at 190° C.for 3 hours. After cooling, it is distilled in vacuo. 25.0 g (29%) ofproduct are obtained as a colourless liquid at 35° C. under 0.25 mbar;n_(D) ²⁰ =1.532. MS: M⁺ =224.

Elemental analysis: calculated C 91.01; H 8.99; found C 90.94; H 9.01.

EXAMPLE A'5

Preparation of Compound No.66

80.2 g (0.50 mol) of cyclododecene and 33.05 g (0.25 mol) ofdicyclopentadiene are mixed in an autoclave and the mixture is heated at190° C. for 8 hours. After cooling, it is distilled in vacuo. 8.10 g(7%) of product are obtained as a colourless liquid at 61° C. under 0.12mbar; n_(D) ²⁰ =1.528. MS: M⁺ =232.

Elemental analysis: calculated C 87.86; H 12.14; found C 87.98; H 11.72.

EXAMPLE A'6

Preparation of Compound No. 68

104.25 g (1.5 mol) of isoprene (98%), 208.7 g (1.5 mol) ofdicyclopentadiene (95%) and 1.0 g of tert-butyl-pyrocatechol are mixedand the mixture is heated at 200° C. for 8 h under N₂ with stirring inan autoclave. After cooling, the semisolid mass is distilled under ahigh vacuum. Boiling point: 60° C. (0.07 mbar). Yield: 202.4 g (67.4%).n_(D) ²⁰ =1.53

Elemental analysis: calculated C 89.94; H 10.06 found C 89.85; H 10.08

EXAMPLE A'7

Preparation of Compound No. 69

139.2 g (1.0 mol) of dicyclopentadiene (95%), 194.2 g (2.0 mol) of2-norbornene (97%) and 3.0 g of tert-butyl-pyrocatechol are mixed andthe mixture is heated at 230° C. for 2 h under N₂ with stirring in anautoclave. After cooling, the semisolid mass is distilled under a highvacuum. Boiling point: 65° C. (0.065 mbar). Yield: 69.0 9 (21.5%). n_(D)²⁰ =1.54

Elemental analysis: calculated C 89.93; H 10.07 found C 90.07; H 9.88

B) Preparation of Crosslinked Polymers.

The catalysts used are:

A) W(═NC₆ H₅)[OC(CH₃)₃ ][CH₂ Si((CH₃)₃ ]₂ Cl

B) W(═NC₆ H₅)[OCCH₃ (CF₃)₂ ][CH₂ Si((CH₃)₃ ]₂

C) RuCl₂ (p-cumene)P(C₆ H₁₁)₃

EXAMPLE B1

The compound according to Example A1 is mixed with 0.7% by weight ofcatalyst A and the mixture is poured into a glass mould. It is thenirradiated at room temperature in a UV oven for 30 minutes (4 tubes of100 W output) and then subjected to thermal polymerization at 80° C. for1 hour. A dimensionally stable sheet, T_(g) 75° C. (determined by meansof differential scanning calorimetry) is obtained. The polymer swells intoluene without dissolving. The low degree of swelling of 44% indicatesa high crosslinking density.

EXAMPLE B2

The mixture according to Example B1 is irradiated only with a 200 Wmercury medium-pressure vapour lamp. A dimensionally stable sheet, T_(g)60° C., is obtained. The degree of swelling in toluene is 54%.

EXAMPLE B3

The procedure is as in Example B1, but with 1% by weight of catalyst andan additional thermal after-curing at 100° C. for 30 minutes. Adimensionally stable sheet with a density of 1.06 g/cm³, a T_(g) of 125°C. and a modulus of elasticity of 2210 N/mm² is obtained. The Shore Dhardness is 85 and the degree of swelling in toluene is 54%.

EXAMPLE B4

The compound according to Example A1 is mixed with 1% by weight ofcatalyst B and the mixture is poured into a glass mould. It isirradiated at room temperature in a UV oven according to Example B1 for2 hours and then polymerized at 80° C. for 30 minutes, at 100° C. for 30minutes and at 120° C. for 30 minutes. A dimensionally stable sheet witha density of 1.06 g/cm³, a T_(g) of 125° C. and a modulus of elasticityof 2390 N/mm² is obtained; the maximum stress is 40.4 N/mm², the maximumextension is 2.0% and the impact strength (according to Charpy) is 8.9kJ/m². The degree of swelling in toluene is 2000%.

EXAMPLES B5 TO B13

The monomer prepared according to Example [lacuna] is mixed with 0.5% byweight of catalyst C and the mixture is poured into a glass mould.Thermal curing is carried out at 60° C. for 1 h, at 80° C. for 1 h, at100° C. for 1 h and 120° C. for 2 h. After-curing take place at 150° C.for 2 h. The following table shows the results.

    ______________________________________                                        Example Monomer   T.sub.g                                                                              Swelling T.sub.g *                                                                          Swelling*                              ______________________________________                                        B5      A1        104    34       117  16                                     B6      A2        100    28       120  9                                      B7      A3        1      180      8    172                                    B8      A'1       122    85       143  76                                     B9      A'3       --     45       15   44                                     B10     A'4       111    55       118  52                                     B11     A'5       117    88       124  87                                     B12     A'6       22     53       29   53                                     B13     A'7       135    81       156  90                                     ______________________________________                                         T.sub.g : ° C.;                                                        swelling: in toluene;                                                         *following aftercuring                                                   

We claim:
 1. A composition comprisinga) at least one compound of formulaI

    (A).sub.n --B                                              (I)

in which A is the radical of a strained cycloolefin, B is a direct bondor an n-valent bridging group, and n is an integer from 2 to 8, and b) acatalytic amount of a one-component catalyst for metathesispolymerization which can be activated by heat or radiation selected fromthe group consisting of ruthenium and osmium compounds which contain atleast one phosphine group, at least one photolabile ligand, andoptionally neutral ligands bonded to the metal atom, a total of 2 to 5ligands being bonded, and which contain acid anions for chargebalancing.
 2. A composition according to claim 1, characterized in thatthe strained olefins are monocyclic or polycyclic fused and/or bridgedring systems which are unsubstituted or substituted and can containheteroatoms O, S, N or Si in one or more rings and/or fused alicyclic,aromatic or heteroaromatic rings.
 3. A composition according to claim 2,characterized in that the individual rings contain 3 to 16 ring members.4. A composition according to claim 2, characterized in that the ringscontain 3 to 12 ring members.
 5. A composition according to claim 2,characterized in that the rings contain 3 to 8 ring members.
 6. Acomposition according to claim 1, characterized in that the radical of astrained cycloolefin corresponds to the formula II ##STR30## Q₁ is aradical having at least one carbon atom which, together with the--CH═CQ₂ group, forms an at least 3-membered alicyclic ring whichoptionally contains one or more heteroatoms chosen from the groupconsisting of silicon, phosphorus, oxygen, nitrogen and sulfur; andwhich is unsubstituted or substituted by halogen, ═O, --CN, --NO₂, R₁ R₂R₃ Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃(M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀ alkly, C₁ -C₂₀ hydroxyalkyl, C₁-C₂₀ haloalkyl, C₁ -C₆ cyanoalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇-C₁₆ aralkyl, C₃ -C₆ heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆heteroaralkyl or R₄ -X-; or in which two adjacent C atoms aresubstituted by --CO--O--CO-- or --CO--NR₅ --CO--; or in which anaromatic or heteroaromatic ring and/or further alicyclic rings which isunsubstituted or substituted by halogen, --CN, --NO₂, R₆ R₇ R₈Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃(M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀hydroxyalkyl, C₁ -C₆ cyanoalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇-C₁₆ aralkyl, C₃ -C₆ heterocycloalkyl, C₃ -C₆ heteroaryl, C₄ -C₁₆heteroaralkyl or R₁₃ -X₁ - are are optionally fused onto adjacent carbonatoms of the alicyclic ring;X and X₁ independently of one another are--O--, --S--, --CO--, --SO--, --SO₂ --, --O--C(O)--, --C(O)--O--,--C(O)--NR₅ --, --NR₁₀ --C(O)--, --SO₂ --O-- or --O--SO₂ --; R₁, R₂ andR₃ independently of one another are C₁ -C₁₂ alkyl, C₁ -C₁₂perfluoroalkyl, phenyl or benzyl; R₄ and R₁₃ independently are C₁ -C₂₀alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆-C₁₆ aryl or C₇ -C₁₆ aralkyl; R₅ and R₁₀ independently of one anotherare hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl, where the alkyl groups inturn are unsubstituted or substituted by C₁ -C₁₂ alkoxy or C₃ -C₈cycloalkyl; R₆, R₇ and R₈ independently of one another are C₁ -C₁₂alkyl, C₁ -C₁₂ perfluoroalkyl, phenyl or benzyl; M is an alkali metaland M₁ is an alkaline earth metal; and u is 0 or 1;where the alicyclicring formed with Q₁ optionally contains further non-aromatic doublebonds; Q₂ is hydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₁₂ alkoxy,halogen, --CN or R₁₁ -X₂ ; R₁₁ is C₁ -C₂₀ alkyl, C₁ C₂₀ haloalkyl, C₁-C₂₀ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl or C₇ -C₁₆ aralkyl;X₂ is --C(O)--O-- or --C(O)--NR₁₂ --; R₁₂ is hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl;where the abovementioned cycloalkyl, heterocycloalkyl,aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted orsubstituted by C₁ -C₁₂ alkyl, C₁ -C₁₂ alkoxy, --NO₂, --CN or halogen,and where the heteroatoms of the abovementioned heterocycloalkyl,heteroaryl and heteroaralkyl groups are chosen from the group consistingof --O--, --S--, --NR₉ -- and --N═; and R₉ is hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl.
 7. A composition according to claim 6, characterizedin that, in formula II, Q₂ is hydrogen.
 8. A composition according toclaim 6, characterized in that, in formula II, the alicyclic ring whichQ₁ forms together with the --CH═CQ₂ -- group contains 3 to 8 ring atoms,the ring being a monocyclic, bicyclic, tricyclic or tetracyclic ringsystem.
 9. A composition according to claim 6, characterized in that theradical of a strained cycloolefin corresponds to the formula II, inwhichQ₁ is a radical with at least one carbon atom which, together withthe --CH═CQ₂ -- group, forms a 3- to 20-membered alicyclic ring whichoptionally contains one or more heteroatoms chosen from the groupconsisting of silicon, oxygen, nitrogen and sulfur; and which isunsubstituted or substituted by halogen, ═O, --CN, --NO₂, R₁ R₂ R₃Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃(M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂hydroxyalkyl, C₁ -C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇-C₁₂ aralkyl, C₃ -C₆ heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₁₂heteroaralkyl or R₄ -X-; or in which two adjacent C atoms in thisradical Q₁ are substituted by --CO--O--CO-- or --CO--NR₅ --CO--; or inwhich an a romatic or heteroaromatic ring and/or further alicyclic ringswhich are unsubstituted or substituted by halogen, --CN, --NO₂, R₆ R₇ R₈Si--, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₁-C₄ cyanoaklyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇ -C₁₂ aralkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₁₂ heteroaralkyl or R₁₃ --X₁-- are optionally fused onto adjacent carbon atoms; X and X₁independently of one another are --O--, --S--, --CO--, --SO--, --SO₂ --,--O--C(O)--, --C(O)--O--, --C(O)--NR₅ --, --NR₁₀ --C(O)--, --SO₂ --O--and --O--SO₂ --; and R₁, R₂ and R₃ independently of one another are C₁-C₆ alkyl, C₁ -C₆ perfluoroalkyl, phenyl or benzyl; M is an alkali metaland M₁ is an alkaline earth metal; R₄ and R₁₃ independently of oneanother are C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₃-C₈ cycloalkyl, C₆ -C₁₂ aryl or C₇ -C₁₂ aralkyl; R₅ and R₁₀independently of one another are hydrogen, C₁ -C₆ alkyl, phenyl orbenzyl, where the alkyl groups in turn are unsubstituted or substitutedby C₁ -C₆ alkoxy or C₃ -C₆ cycloalkyl; R₆, R₇ and R₈ independently ofone another are C₁ -C₆ alkyl, C₁ -C₆ perfluoroalkyl, phenyl or benzyl; uis 0 or 1;where the alicyclic ring formed with Q₁ optionally containsfurther non-aromatic double bonds; Q₂ is hydrogen, C₁ -C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁ -C₆ alkoxy, halogen, --CN or R₁₁ --X₂ --; R₁₁ is C₁-C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₆ cycloalkyl,C₆ -C₁₂ aryl or C₇ -C₁₂ aralkyl; X₂ is --C(O)--O-- or --C(O)--NR₁₂ ; andR₁₂ is hydrogen, C₁ -C₆ alkyl, phenyl or benzyl;and where thecycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl andheteroaralkyl groups are unsubstituted or substituted by C₁ -C₆ alkyl,C₁ -C₆ alkoxy, --NO₂, --CN or halogen, and where the heteroatoms of theheterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen fromthe group consisting of --O--, --S--, --NR₉ -- and --N═; and R₉ ishydrogen, C₁ -C₆ alkyl, phenyl or benzyl.
 10. A composition according toclaim 1, characterized in that the radical of a strained cycloolefincorresponds to the formula II, in whichQ₁ is a radical with at least onecarbon atom which, together with the --CH═CQ₂ -- group, forms a 3- to10-membered alicyclic ring which optionally contains a heteroatom chosenfrom the group consisting of silicon, oxygen, nitrogen and sulfur and isunsubstituted or substituted by halogen, --CN, --NO₂, R₁ R₂ R₃ Si--,--COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/12), --SO₃ (M₁)_(1/12), --PO₃(M₁)_(1/12), C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ hydroxyalkyl, C₁ -C₄cyanoalkyl, C₃ -C₆ cycloalkyl, phenyl, benzyl or R₄ -X-; or in which anaromatic or heteroaromatic ring which is unsubstituted or substituted byhalogen, --CN, --NO₂, R₆ R₇ R₈ Si--, --COOM, --SO₃ M, --PO₃ M,--COO(M₁)_(1/12), --SO₃ (M₁)_(1/12), --PO₃ (M₁)_(1/12), C₁ -C₆ alkyl, C₁-C₆ haloalkyl, C₁ -C₆ hydroxyalkyl, C₁ -C₄ cyanoalkyl, C₃ -C₆cycloalkyl, phenyl, benzyl or R₁₃ --X₁ -- is optionally fused ontoadjacent carbon atoms; R₁, R₂ and R₃ independently of one another are C₁-C₄ alkyl, C₁ -C₄ perfluoroalkyl, phenyl or benzyl; M is an alkali metaland M₁ is an alkaline earth metal; R₄ and R₁₃ independently of oneanother are C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ hydroxyalkyl or C₃-C₆ cycloalkyl; X and X₁ independently of one another are --O--, --S--,--CO--, --SO-- or --SO₂ --; R₆, R₇ and R₈ independently of one anotherare C₁ -C₄ alkyl, C₁ -C₄ perfluoroalkyl, phenyl or benzyl; and Q₂ ishydrogen.
 11. A composition according to claim 1, characterized in thatthe cycloolefin radical of the formula II is unsubstituted orsubstituted cyclopropenyl, cyclobutenyl, cyclopentenyl, cycloheptenyl,cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl,cyclooctadienyl and norbornenyl or norbornenyl derivatives.
 12. Acomposition according to claim 6, characterized in that the cycloolefinradical of the formula II is a radical of the formula III ##STR31## inwhich X₃ is --CHR₁₆ --, oxygen or sulfur;R₁₄ and R₁₅ independently ofone another are hydrogen, --CN, trifluoromethyl, (CH₃)₃ Si--O--, (CH₃)₃Si-- or --COOR₁₇ ; and R₁₆ and R₁₇ independently of one another arehydrogen, C₁ -C₁₂ -alkyl, phenyl or benzyl; or of the formula IV##STR32## in which X₄ is --CHR₁₉ --, oxygen or sulfur;R₁₉ is hydrogen,C₁ -C₁₂ alkyl, phenyl or benzyl; and R₁₈ is hydrogen, C₁ -C₆ alkyl orhalogen.
 13. A composition according to claim 6, characterized in thatthe cycloolefin radical of the formula II is norbornenyl of the formula##STR33##
 14. A composition according to claim 1, characterized in that,in formula I, n is an integer from 2 to
 6. 15. A composition accordingto claim 1, characterized in that, in formula I, n is an integer from 2to
 4. 16. A composition according to claim 1, characterized in that, informula I, n is the number 2 or
 3. 17. A composition according to claim1, characterized in that, in formula I, B is an n-valent bridging group.18. A composition according to claim 1, characterized in that thebridging group corresponds to the formula V

    --X.sub.5 --R.sub.20 --X.sub.6 --                          (V)

in which X₅ and X₆ independently of one another are a direct bond,--O--, --CH₂ --O--, --C(O)O--, --O(O)C--, --CH₂ --O(O)C--, --C(O)--NR₂₁--, --R₂₁ --N--(O)C--, --NH--C(O)--NR₂₁ --, --O--C(O)--NH--, --CH₂--O--C(O)--NH-- or --NH--C(O)--O-- and R₂₀ is C₂ -C₁₈ alkylene, C₅ -C₈cycloalkylene which is unsubstituted or substituted by C₁ -C₄ alkyl orC₁ -C₄ alkoxy, C₆ -C₁₈ arylene or C₇ -C₁₉ aralkylene which areunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, orpolyoxaalkylene having 2 to 12 oxaalkylene units and 2 to 6 C atoms inthe alkylene, and R₂₁ is H or C₁ -C₆ alkyl.
 19. A composition accordingto claim 15, characterized in that, in formula V,a) X₅ and X₆ are adirect bond and R₂₀ is C₂ -C₁₈ alkylene, or b) X₅ and X₆ are --O--,--CH₂ --O--, --C(O)O--, --O(O)C--, --CH₂ --O(O)C--, --C(O)--NR₂₁ --,--O--C(O)--NH-- or --CH₂ --O--C(O)--NH--, and R₂₀ is C₂ -C₁₂ alkylene,phenylene, naphthylene or benzylene which are unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or --R₂₂ --(O--R₂₂ --)_(x)--OR₂₂ --, in which x is a number from 2 to 4, and R₂₂ is --C₂ -C₄alkylene.
 20. A composition according to claim 18, characterized in thatthey are chosen from the following group of compounds: ##STR34##
 21. Acomposition according to claim 1, characterized in that the bridginggroup corresponds to the formula VI in whichX₅, X₆ and X₇ are --O--,--CH₂ --O--, --C(O)O--, --O(O)C--, --CH₂ --O(O)C--, --C(O)--NR₂₁ --,--R₂₁ N--(O)C--, --NH--C(O)--NR₂₁ --, --O--C(O)--NH--, --CH₂--O--C(O)--NH-- or --NH--C(O)--O--, and R₂₃ is a trivalent aliphatichydrocarbon radical having 3 to 20 C atoms, a trivalent cycloaliphaticradical which has 3 to 8 ring C atoms and is unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or a trivalent aromaticradical which has 6 to 18 C atoms and is unsubstituted or substituted byC₁ -C₄ alkyl or C₁ -C₄ alkoxy, a trivalent araliphatic radical which has7 to 19 C atoms and is unsubstituted or substituted by C₁ -C₄ alkyl orC₁ -C₄ alkoxy, or a trivalent heteroaromatic radical which has 3 to 13 Catoms and 1 to 3 heteroatoms from the group consisting of --O--, --N--and --S-- and is unsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄alkoxy, and R₂₁ is H or C₁ -C₆ alkyl.
 22. A composition according toclaim 21, characterized in that X₅, X₆ and X₇ are --O--, --CH₂ --O--,--C(O)O--, --O(O)C--, --CH₂ --O(O)C--, --C(O)--NR₂₁ --, --CH₂--O--C(O)--NH-- or --O--C(O)--NH--.
 23. A composition according to claim21, characterized in that the radicals R₂₃ are derived from triols;cyanuric acid; triamines; tricarboxylic acids or triisocyanates.
 24. Acomposition according to claim 21, characterized in that they are chosenfrom the following group of compounds ##STR35##
 25. A compositionaccording to claim 1, characterized in that the bridging groupcorresponds to the formula VII in whichX₅, X₆, X₇ and X₈ are --C(O)O--,--CH₂ --O(O)C-- or --C(O)--NR₂₁ -- and R₂₄ is a tetravalent aliphatichydrocarbon radical having 4 to 20 C atoms, a tetravalent cycloaliphaticradical which has 4 to 8 ring C atoms and is unsubstituted orsubstituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or a tetravalent aromaticradical which has 6 to 18 C atoms and is unsubstituted or substituted byC₁ -C₄ alkyl or C₁ -C₄ alkoxy, a tetravalent araliphatic radical whichhas 7 to 19 C atoms and is unsubstituted or substituted by C₁ -C₄ alkylor C₁ -C₄ alkoxy, or a tetravalent heteroaromatic radical which has 3 to13 C atoms and 1 to three heteroatoms, from the group consisting of--O--, --N-- and --S-- and is unsubstituted or substituted by C₁ -C₄alkyl or C₁ -C₄ alkoxy, and R₂₁ is H or C₁ -C₆ alkyl.
 26. A compositionaccording to claim 25, characterized in that the radicals R₂₄ arederived from pentaerythritol, pyromellitic acid and3,4,3',4'-biphenyltetracarboxylic acid.
 27. A composition according toclaim 25, characterized in that they are ##STR36##
 28. A compositionaccording to claim 1, characterized in that the compounds of the formulaI contain only carbon and hydrogen atoms.
 29. Composition according toclaim 1, characterized in that the phosphine ligands correspond to theformulae XXIII or XXIIIa.

    PR.sub.91 R.sub.92 R.sub.93                                (XXIII),

    R.sub.91 R.sub.92 P-Z.sub.1 -PR.sub.91 R.sub.92            (XXIIIa)

in which R₉₁, R₉₂ and R₉₃ independently of one another are H, C₁ -C₂₀alkyl, C₄ -C₁₂ cycloalkyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, or C₆ -C₁₆ aryl which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆alkoxy, or C₇ -C₁₆ aralkyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy; the radicals R₉₁ and R₉₂together are tetra- or pentamethylene, which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, ortetra- or pentamethylene, which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy and fused with 1 or 21,2-phenylene, and R₉₃ has the meaning given above; and Z₁ is linear orbranched C₂ -C₁₂ alkylene which is unsubstituted or substituted by C₁-C₄ alkoxy, 1,2-or 1,3-cycloalkylene which has 4 to 8 C atoms and isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or 1,2 or1,3-heterocycloalkylene which has 5 or 6 ring members and one heteroatomfrom the group consisting of O or N and is unsubstituted or substitutedby C₁ -C₄ alkyl or C₁ -C₄ alkoxy.
 30. Composition according to claim 1,characterized in that the one-component catalyst is a divalent-cationicruthenium or osmium compound with a metal atom to which are bonded, 1 to3 tertiary phosphine ligands with, in the case of the rutheniumcompounds, sterically exacting substituents, optionally non-photolabileneutral ligands and anions for charge balancing, with the proviso that,in ruthenium (trisphenylphosphine) dihalides or hydride-halides, thephenyl groups are substituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ haloalkyl or C₁-C₁₈ alkoxy.
 31. Composition according to claim 30, characterized inthat the phosphine ligands correspond to the formulae XXIII or XXIIIa

    PR.sub.91 R.sub.92 R.sub.93                                (XXIII),

    R.sub.91 R.sub.92 P-Z.sub.1 -PR.sub.91 R.sub.92            (XXIIIa),

in which R₉₁, R₉₂ and R₉₃ independently of one another are H, C₁ -C₂₀alkyl, C₄ -C₁₂ cycloalkyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, or C₆ -C₁₆ aryl which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆alkoxy, or C₇ -C₁₆ aralkyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy; the radicals R₉₁ and R₉₂together are tetra- or pentamethylene, which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy, ortetra- or pentamethylene, which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ haloalkyl or C₁ -C₆ alkoxy and fused with 1 or 21,2-phenylene, and R₉₃ has the meaning given above; and Z, is linear orbranched C₂ -C₁₂ alkylene which is unsubstituted or substituted by C₁-C₄ alkoxy, 1,2- or 1,3-cycloalkylene which has 4 to 8 C atoms and isunsubstituted or substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxy, or 1,2 or1,3-heterocycloalkylene which has 5 or 6 ring members and one heteroatomfrom the group consisting of O or N and is unsubstituted or substitutedby C₁ -C₄ alkyl or C₁ -C₄ alkoxy.
 32. Composition according to claim 1,characterized in that the one-component catalyst is present in an amountof from 0.001 to 20 mol %, based on the amount of the monomer.